JP2012103367A - Charging member, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charging member of an electrophotographic device, capable of suppressing degradation in the charging member by energizing the member in various environments from low temperature and low humidity to high temperature and high humidity, suppressing generation of a sandy image, maintaining favorable images for a long period of time and achieving a long service life.SOLUTION: The charging member comprises a conductive substrate and a surface layer. The surface layer contains at least a binder resin and conductive composite particles comprising conductive particles coated with a substance that contains a compound having a siloxane dendrimer structure in a vinyl group or in a side chain of a vinyl polymer.

Description

  The present invention relates to a charging member for charging the surface of an electrophotographic photosensitive member to a predetermined potential.

  In an electrophotographic apparatus, as a method of charging the surface of an electrophotographic photosensitive member (hereinafter, also simply referred to as “photosensitive member”), a roller-shaped charging member (hereinafter referred to as “contacting member”) disposed in contact with the surface of the photosensitive member. A contact charging method using a charging roller) is often used. Usually, the charging roller generally has a configuration having a conductive elastic layer and a conductive surface layer for surface protection in order to increase the area of the contact portion with the photoreceptor.

  By the way, in the charging member having a surface layer made conductive by containing conductive particles, the electric resistance value of the charging member gradually changes as the voltage is applied for a long time. There is. This tendency is particularly remarkable in a low temperature and low humidity environment.

  More specifically, when a voltage is continuously applied to the charging member, the electrical resistance partially increases, the charging performance of the part decreases, and accordingly, the charged potential on the surface of the photosensitive member becomes uneven. Sometimes. Such unevenness of the charged potential may be reflected on the electrophotographic image. For such a problem, Patent Document 1 discloses a technique of treating the surface of conductive particles with a coupling agent.

Japanese Patent Laid-Open No. 10-254217

However, according to the study by the present inventors, even a charging member having a conductive surface layer containing conductive particles surface-treated with a coupling agent can be used under harsh conditions such as low temperature and low humidity. In the case where a DC voltage was applied to the charging member for a long period of time, a change in electric resistance with time was recognized.
Therefore, an object of the present invention is to provide a charging member that can further suppress fluctuations in electrical resistance even under severe conditions.

（式（１）中、Ｒ１は水素原子または炭素原子数１以上４以下のアルキル基である。Ｇは式（２）で表わされる構造を有する基である。）

（式（２）中、Ａは炭素原子数２以上１０以下のアルキレン基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基および下記式（６）〜式（８）で表わされる２価の基からなる群から選ばれる基を示す。ａは０または１である。Ｅ１、Ｅ２およびＥ３は各々独立に下記式（３）で表わされる基を示す。）

（式（６）〜式（８）中、Ｒ８、Ｒ９およびＲ１１は各々独立に、炭素原子数１以上１０以下のアルキレン基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基である。式（８）中、Ｒ１０は炭素原子数１以上１０以下のアルキル基、炭素原子数１以上１０以下のアルコキシル基、炭素原子数６以上２０以下のアリール基、炭素原子数７以上２０以下のアラルキル基、アリル基またはハロゲン原子である。ｄは０以上４以下の整数である。ｅは０または１である。）

（式（３）中、ｋは０または１である。ｈは０以上３以下の整数である。Ｚ１は炭素原子数２以上１０以下のアルキレン基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基および下記式（１５）〜（１７）で表わされる２価の基からなる群から選ばれる基を示す。Ｒ３、Ｒ４、Ｒ６およびＲ７は各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。Ｒ５は炭素原子数１以上１０以下のアルコキシ基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェノキシ基、下記式（２０）または下記式（２１）で示される基である。Ｘは、水素原子、炭素原子数１以上１０以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、アリル基、ビニル基、下記式（１８）で表わされる基および下記式（１９）で表わされる基からなる群から選ばれる基である。）

（式（１５）〜式（１７）中、Ｒ１５、Ｒ１６およびＲ１７は各々独立に、炭素原子数１以上１０以下のアルキレン基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基である。ｐは０以上３以下の整数である。）

（式（１８）中、Ｒ１８は、炭素原子数１以上６以下のアルキレン基である。）

（式（１９）中、ｒは０または１であり、ｓは０以上３以下の整数である。Ｚ２は炭素原子数２以上１０以下のアルキレン基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基および上記式（１５）〜（１７）で表わされる２価の基からなる群から選ばれる基を示す。Ｒ１９、Ｒ２０、Ｒ２２およびＲ２３は各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。Ｒ２１は炭素原子数１以上１０以下のアルコキシ基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェノキシ基、下記式（２０）または下記式（２１）で示される基である。
Ｘ２は、水素原子、炭素原子数１以上１０以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、アリル基、ビニル基、上記式（１８）で表わされる基および上記式（１９）で表わされる基からなる群から選ばれる基である。上記式（３）においてＸが下記式（１９）である場合、式（１９）で表わされる基の繰り返しの数は１以上１０以下であり、かつ、最末端を構成している式（１９）中のＸ２は、水素原子、炭素原子数１以上１０以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、アリル基、ビニル基または上記式（１８）で示される基である。）

（式（２０）中、Ｒ２４は、炭素原子数１以上６以下のアルキレン基である。）

（式（２１）中、Ｒ２５、Ｒ２６およびＲ２７は、各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。） According to the present invention, there is provided a charging member having a conductive substrate and a surface layer, wherein the surface layer is coated with a binder resin and a compound having the surface of the conductive particles having a unit represented by the following formula (1). A charging member containing conductive composite particles is provided:

(In formula (1), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. G is a group having a structure represented by formula (2).)

(In the formula (2), A is an alkylene group having 2 to 10 carbon atoms, a phenylene group which may be substituted at least one selected from a methyl group and an ethyl group, and the following formulas (6) to (8): A represents 0 or 1. E1, E2 and E3 each independently represent a group represented by the following formula (3).)

(In the formulas (6) to (8), R8, R9 and R11 may each independently be substituted with at least one selected from an alkylene group having 1 to 10 carbon atoms, a methyl group and an ethyl group. In formula (8), R10 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms. And an aralkyl group, an allyl group or a halogen atom of 20 or less, d is an integer of 0 or more and 4 or less, and e is 0 or 1.)

(In Formula (3), k is 0 or 1. h is an integer of 0 or more and 3 or less. Z1 is at least one selected from an alkylene group having 2 to 10 carbon atoms, a methyl group, and an ethyl group. A group selected from the group consisting of an optionally substituted phenylene group and a divalent group represented by the following formulas (15) to (17): R3, R4, R6 and R7 each independently has 1 carbon atom. Represents an optionally substituted phenyl group selected from an alkyl group having 5 or less and a methyl group and an ethyl group, and R5 is selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group, and an ethyl group. A phenoxy group which may be substituted at least on the other hand, a group represented by the following formula (20) or the following formula (21), wherein X is a hydrogen atom, having 1 to 10 carbon atoms. It consists of a phenyl group, an allyl group, a vinyl group, a group represented by the following formula (18) and a group represented by the following formula (19), which may be substituted at least one selected from an alkyl group, a methyl group and an ethyl group A group selected from the group.)

(In Formula (15) to Formula (17), R15, R16, and R17 may each independently be substituted with at least one selected from an alkylene group having 1 to 10 carbon atoms, a methyl group, and an ethyl group. (It is a phenylene group. P is an integer of 0 or more and 3 or less.)

(In formula (18), R18 is an alkylene group having 1 to 6 carbon atoms.)

(In the formula (19), r is 0 or 1, and s is an integer of 0 to 3. Z2 is at least one selected from an alkylene group having 2 to 10 carbon atoms, a methyl group, and an ethyl group. R19, R20, R22 and R23 each independently represents a group selected from the group consisting of an optionally substituted phenylene group and a divalent group represented by the above formulas (15) to (17). Represents an optionally substituted alkyl group having 5 or less or a phenyl group optionally selected from a methyl group and an ethyl group, and R21 is selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. A phenoxy group which may be substituted at least on one side, a group represented by the following formula (20) or the following formula (21).
X2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, represented by the above formula (18). And a group selected from the group consisting of groups represented by the above formula (19). In the formula (3), when X is the following formula (19), the number of repeating groups represented by the formula (19) is 1 or more and 10 or less, and the most terminal formula (19) X2 therein is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, or the above formula (18) It is group shown by these. )

(In the formula (20), R24 is an alkylene group having 1 to 6 carbon atoms.)

(In the formula (21), R25, R26 and R27 each independently represent an optionally substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group. )

  According to the present invention, the conductive particles in the surface layer are fixed in the binder, and the movement of the conductive particles in the surface layer is suppressed even by applying a DC voltage for a long time. As a result, it is possible to obtain a charging member whose charging performance is stable over a long period of time.

It is sectional drawing of the charging roller of this invention. It is sectional drawing of another charging roller of this invention. It is sectional drawing of another charging roller of this invention. 1 is a schematic configuration diagram illustrating an embodiment of an electrophotographic apparatus of the present invention. It is a block diagram showing embodiment of one example of the process cartridge of this invention. It is explanatory drawing of the measuring method of the electrical resistance value of a charging roller. It is the schematic showing the contact state of the charging roller and photoconductor at the time of a discharge idling acceleration test. It is explanatory drawing of the specific structure which concerns on Formula (3).

As a result of intensive studies, the present inventors use conductive composite particles in which conductive particles added to the surface layer of the charging member are coated with a substance containing a compound having a structure represented by the formula (1) described later. By doing so, it was found that a charging member capable of achieving a long life can be obtained.
That is, the present inventors have found that the change in electrical resistance of the surface layer over time is caused by the oxidation of the conductive particles added to the surface layer and the expansion and contraction of the surface layer accompanying repeated use of the charging member. It is presumed that this is due to the cutting of the conductive path due to the change in the location of the conductive particles.
On the other hand, since the compound according to the formula (1) covering the conductive particles has a very bulky structure, the composite conductive particles are considered to be hardly oxidized.

  In addition, the compound has a siloxane dendrimer structure (a highly branched structure in which a siloxane bond and a silalkylene bond are alternately arranged) in a vinyl group or a side chain of a vinyl polymer. It has a structure. With such a structure, the composite conductive particles and the binder are intertwined well, and the position of the composite conductive particles in the surface layer is fixed. It is considered that the movement of the conductive particles is suppressed by repeated expansion and contraction of the surface layer and voltage application. For these reasons, it is considered that the charging performance of the charging member according to the present invention does not easily change over time even after repeated use under various environments.

<Configuration of charging member>
The charging member of the present invention comprises at least a conductive substrate and a surface layer provided on the conductive substrate.
1 to 3 show schematic sectional views as an example of the charging member of the present invention. FIG. 1 shows a roller-shaped charging member (charging roller) in which an elastic layer 2 is provided on a conductive substrate 1 and a surface layer 3 is further provided thereon. FIG. 2 shows a charging roller having an intermediate layer 21 between the elastic layer 2 and the surface layer 3. FIG. 3 shows a charging roller having a first intermediate layer 21 and a second intermediate layer 22 between the elastic layer 2 and the surface layer 3.

<Configuration of surface layer>
The surface layer according to the present invention contains a binder and conductive composite particles obtained by coating the conductive particles with a substance containing a compound having a unit represented by the following formula (1).

<Compound having unit represented by formula (1)>
The compound having the unit represented by the formula (1) is a highly branched group in which a vinyl group or a side chain of a vinyl polymer has a siloxane dendrimer structure (a polysiloxane structure is a nucleus, and siloxane bonds and silalkylene bonds are alternately arranged. Structure).
Examples of R1 represented by the formula (1) include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. G is a group having a structure represented by the formula (2).

式（２）で示すＡは、炭素原子数２以上１０以下のアルキレン基、メチル基およびエチル基から選ばれる少なくとも一方で置換されてもよいフェニレン基および下記式（６）〜式（８）で表わされる２価の基からなる群から選ばれる基である。

式（６）〜式（８）中、Ｒ８、Ｒ９、Ｒ１１は各々独立に、炭素原子数１以上１０以下のアルキレン基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基である。式（８）中、Ｒ１０は炭素原子数１以上１０以下のアルキル基、炭素原子数１以上１０以下のアルコキシル基、炭素原子数６以上２０以下のアリール基、炭素原子数７以上２０以下のアラルキル基、アリル基、またはハロゲン原子である。ｄは０以上４以下の整数である。ｅは０または１である。 (In formula (1), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. G is a group having a structure represented by formula (2).)

A in the formula (2) is a phenylene group which may be substituted at least one selected from an alkylene group having 2 to 10 carbon atoms, a methyl group and an ethyl group, and the following formulas (6) to (8): It is a group selected from the group consisting of represented divalent groups.

In the formulas (6) to (8), R8, R9 and R11 are each independently an alkylene group having 1 to 10 carbon atoms, or phenylene which may be substituted at least one selected from a methyl group and an ethyl group It is a group. In formula (8), R10 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Group, an allyl group, or a halogen atom. d is an integer of 0 or more and 4 or less. e is 0 or 1;

  By adopting this structure, it becomes possible to further improve the stability of the compound when the conductive particles are coated.

R8 and R9 are exemplified by an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group, and among them, a methylene group and a propylene group are more preferable.
R10 is exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and among these, a methyl group is more preferable. R11 is exemplified by an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group, and among these, an ethylene group is more preferable.

  E1, E2 and E3 represented by the formula (2) are each independently a group represented by the following formula (3). A is 0 or 1.

  Z1 represented by formula (3) is an alkylene group having 2 to 10 carbon atoms, a phenylene group optionally substituted from at least one selected from a methyl group and an ethyl group, and the following formulas (15) to (17): A linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group, methylmethylene group, methylethylene group, 1-methylpentylene group, 1,4-dimethylbutylene group Such branched alkylene groups are exemplified. Moreover, k shown by Formula (3) is 0 or 1, and h is an integer of 0 or more and 3 or less.

式（１５）〜式（１７）中、Ｒ１５、Ｒ１６、およびＲ１７は各々独立に、炭素原子数１以上１０以下のアルキレン基、または、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基である。ｐは０以上３以下の整数である。 R3, R4, R6 and R7 are each independently a phenyl group which may be substituted at least one selected from an alkyl group having 1 to 5 carbon atoms or a methyl group and an ethyl group.
R5 is a group represented by the following formula (20) or the following formula (21) optionally substituted by at least one selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. .
X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, represented by the following formula (18). And a group selected from the group consisting of groups represented by the following formula (19).

In the formulas (15) to (17), R15, R16, and R17 are each independently substituted with at least one selected from an alkylene group having 1 to 10 carbon atoms, or a methyl group and an ethyl group. It is also a good phenylene group. p is an integer of 0 or more and 3 or less.

  In the formula (3), R3, R4, R6 and R7 are each independently an alkyl group having 1 to 5 carbon atoms or a phenyl group. Among these, a methyl group is more preferable.

Ｒ２４は、炭素原子数１以上６以下のアルキレン基である。

Ｒ２５、Ｒ２６およびＲ２７は、各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。

式（１８）において、Ｒ１８は、炭素原子数１以上６以下のアルキレン基である。

式（１９）において、ｒは０または１であり、ｓは０以上３以下の整数である。
Ｚ２は炭素原子数２以上１０以下のアルキレン基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニレン基および上記式（１５）〜（１７）で表わされる２価の基からなる群から選ばれる基を示す。Ｒ１９、Ｒ２０、Ｒ２２およびＲ２３は各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。Ｒ２１は炭素原子数１以上１０以下のアルコキシ基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェノキシ基、下記式（２０）または下記式（２１）で示される基である。
Ｘ２は、水素原子、炭素原子数１以上１０以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、アリル基、ビニル基、上記式（１８）で表わされる基および上記式（１９）で表わされる基からなる群から選ばれる基である。
上記式（３）においてＸが下記式（１９）である場合、式（１９）で表わされる基の繰り返しの数は１以上１０以下であり、かつ、最末端を構成している式（１９）中のＸ２は、水素原子、炭素原子数１以上１０以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、アリル基、ビニル基または上記式（１８）で示される基である。
ここで、式（３）において、ｋ＝０であって、Ｘが式（１９）であり、かつ、式（１９）で表わされる基の繰り返しの数が１であるときの式（３）の構造を図８（ａ）に示す。また、当該繰り返しの数が３であるときの式（３）の構造を図８（ｂ）に示す。

式（２０）において、Ｒ２４は、炭素原子数１以上６以下のアルキレン基である。

式（２１）において、Ｒ２５、Ｒ２６およびＲ２７は、各々独立に炭素原子数１以上５以下のアルキル基またはメチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基を示す。 R5 is a group represented by the following formula (20) or the following formula (21) optionally substituted by at least one selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. .

R24 is an alkylene group having 1 to 6 carbon atoms.

R25, R26 and R27 each independently represent an alkyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group.

In the formula (18), R18 is an alkylene group having 1 to 6 carbon atoms.

In the formula (19), r is 0 or 1, and s is an integer of 0 or more and 3 or less.
Z2 is an alkylene group having 2 to 10 carbon atoms, a phenylene group which may be substituted at least one selected from a methyl group and an ethyl group, and a divalent group represented by the above formulas (15) to (17). A group selected from the group consisting of: R19, R20, R22 and R23 each independently represents an alkyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group. R21 is a group represented by the following formula (20) or the following formula (21) optionally substituted by at least one selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. .
X2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, represented by the above formula (18). And a group selected from the group consisting of groups represented by the above formula (19).
In the formula (3), when X is the following formula (19), the number of repeating groups represented by the formula (19) is 1 or more and 10 or less, and the most terminal formula (19) X2 therein is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, or the above formula (18) It is group shown by these.
Here, in the formula (3), k = 0, X is the formula (19), and the number of repetitions of the group represented by the formula (19) is 1, The structure is shown in FIG. FIG. 8B shows the structure of the formula (3) when the number of repetitions is 3.

In the formula (20), R24 is an alkylene group having 1 to 6 carbon atoms.

In the formula (21), R25, R26 and R27 each independently represent an optionally substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group.

  In addition, each group in said Formula (3)-(21) may be different groups, as long as the said definition is satisfied in E1, E2, and E3. For example, Z1 in the formula (3) constituting E1 and Z1 in the formula (3) constituting E2 are at least selected from an alkylene group having 2 to 10 carbon atoms, a methyl group, and an ethyl group. On the other hand, it may be different as long as it is a group selected from the group consisting of an optionally substituted phenylene group and a divalent group represented by the following formulas (15) to (17).

  H in the formula (3) is 0, X is a group represented by the formula (19), and the number of repeating groups represented by the formula (19) is 1 or more and 3 or less, and More preferably, r in the formula (19) is 0. By these, the water repellency of a compound can further be improved and the moisture absorption of electroconductive particle can further be suppressed.

More preferably, the compound has a unit represented by the formula (1) and a unit represented by the following formula (4).

  In the formula (4), examples of R2 include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.

  J is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group, the following formulas (9), (10) or (11 ).

式（９）、（１０）中、Ｒ１２およびＲ１３は、各々独立に、炭素原子数１以上６以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基、および前記式（１１）で示される基である。式（１１）中、Ｒ１４は、炭素原子数１以上４以下のアルキル基、メチル基およびエチル基から選ばれる少なくとも一方で置換されていてもよいフェニル基である。ｔは１以上３以下の整数である。 Among these, the structure represented by the following formula (9), (10) or (11) is more preferable.

In formulas (9) and (10), R12 and R13 are each independently a phenyl group optionally substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms, a methyl group and an ethyl group, And a group represented by the formula (11). In formula (11), R14 is a phenyl group which may be substituted at least one selected from an alkyl group having 1 to 4 carbon atoms, a methyl group and an ethyl group. t is an integer of 1 or more and 3 or less.

  By having a structure like a copolymer with a vinyl polymer as shown in the above formula (4), it is easy to coat the surface of the conductive particles, and once coated, it becomes difficult to peel off. The effect of suppressing moisture absorption and oxidation on the surface is further enhanced. In addition, the entanglement with the binder resin of the surface layer is further strengthened, and the slight movement of the conductive particles when electric charges are applied to the conductive particles is suppressed. As a result, even if a voltage is continuously applied for a long time, It becomes possible to obtain a charging member with very little deterioration.

  The molecular weight of the compound of the present invention is a polystyrene-equivalent number average molecular weight of 10,000 or more, more preferably in the range of 20,000 to 2,000,000. When the molecular weight is 10,000 or more, the conductive particles can be sufficiently covered, which is preferable.

（式中、Ｒ１、Ａ、ａ、Ｅ１、Ｅ２およびＥ３は、前記記載の例示と同じである。） The compound can be obtained by polymerizing a compound represented by the following formula (12) or the following formula (12).

(In the formula, R1, A, a, E1, E2, and E3 are the same as those described above.)

An example of the structure represented by Formula (12) is shown in Formula (13) and Formula (14).

  Furthermore, the compound can be obtained by polymerizing a compound represented by the formula (12) and a compound having a vinyl group.

  The compound having a vinyl group may be any compound having a radical polymerizable vinyl group. Of these, lower alkyl (meth) acrylates, aromatic vinyl monomers and amide group-containing vinyl monomers are more preferred. Specifically, examples of the lower alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Examples of the aromatic vinyl type monomer include styrene, vinyl toluene, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate. Examples of the amide group-containing vinyl monomer include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.

  Further, by adjusting the mixing ratio of the compound represented by the formula (12) and the compound having a vinyl group, the content of the unit represented by the formula (1) can be adjusted with respect to the entire compound. it can.

  As a polymerization method for obtaining the compound, a radical polymerization method or an ionic polymerization method is used. Among these, the radical polymerization method is more preferable, and among the radical polymerization methods, the solution polymerization method is more preferable.

  In the solution polymerization method, only a compound represented by the formula (12) or a compound represented by the formula (12) and a compound having a vinyl group are mixed in a solvent in the presence of a radical initiator at 50 ° C. or higher and 150 ° C. or lower. The reaction is carried out under the following temperature conditions.

  Examples of the solvent used at this time include aliphatic hydrocarbons such as hexane, octane, decane, and cyclohexane.

As the radical initiator, conventionally known compounds generally used in radical polymerization methods are used. Specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methyl) are used. Butyronitrile), azobis compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2- An organic peroxide such as ethylhexanoate can be exemplified.
This radical initiator may be used individually by 1 type, and may mix and use 2 or more types. The amount of radical initiator used is preferably in the range of 0.1 parts by mass or more and 5 parts by mass or less when the total amount of the compounds to be polymerized is 100 parts by mass.

A chain transfer agent can be added during the polymerization. Specific examples of this chain transfer agent are listed below. Mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group.
The amount of such chain transfer agent is preferably 0.001 to 15 parts by mass, more preferably 0.01 to 10 parts by mass, when the total amount of the compounds to be polymerized is 100 parts by mass. Or less. In addition, when manufacturing the polymer of this invention, it is preferable to remove the unreacted vinyl-type compound which remain | survives by carrying out pressure reduction treatment under a heating after superposition | polymerization.

<Material containing a compound having a unit represented by the formula (1) that coats conductive particles>
In the present invention, the substance covering the conductive particles may contain at least a compound having a unit represented by the formula (1), but preferably contains 50% or more. More preferably, it contains 80% or more.

<Conductive particles>
As the conductive particles, electron conductive particles or ion conductive particles can be used.

  Electroconductive particles include metal-based fine particles such as aluminum, palladium, iron, copper and silver, metal oxides such as titanium oxide, tin oxide, zinc oxide and silicon oxide, and different metals and different metal oxides. Metal oxides doped with such materials, metal-based fine particles as described above, and composite particles surface-treated by electrolytic treatment, spray coating, mixed shaking, furnace black, thermal black, Examples thereof include carbon powders such as acetylene black, ketjen black, PAN (polyacrylonitrile) -based carbon, and pitch-based carbon. These electronic conductive particles can be used alone or in combination of two or more.

As ion conductive particles, the following low molecular ion conductive agents are kneaded into a resin having a polyether bond (for example, polyethylene oxide, polypropylene oxide, polyether amide, polyether ester amide, polyether ester). Can be illustrated.
Examples of the low molecular ion conductive agent include inorganic ionic substances such as lithium perchlorate, sodium perchlorate, and calcium perchlorate.

As the conductive particles, hybrid particles obtained by combining the above electronic conductive particles and ionic conductive particles can also be used.
As a method for producing such hybrid particles, a method in which electron conductive particles are previously kneaded with ion conductive particles such as polyether ester amide, polyester amide, polyether amide, and polyether ester to form a pellet is known. The desired hybrid particles are obtained by pulverization by the above method (for example, mechanical pulverization, freeze pulverization) and classification as necessary.
Moreover, the following methods are mentioned as a method of obtaining the hybrid particle nearer spherical. A composite resin (hereinafter referred to as composite resin A) in which electronic conductive particles are kneaded with ions such as polyether ester amide, polyester amide, polyether amide, and polyether ester in advance is not compatible with composite resin A. A resin (this is referred to as “resin B”) is mixed, and the composite resin A and the resin B are uniformly mixed and dispersed. Thereafter, the mixture is cooled to a temperature equal to or lower than the melting point, and a developing solvent which is incompatible with the composite resin A but is compatible with the resin B and the resin mixture are mixed to obtain a suspension of resin particles. And the particle | grains which consist of composite resin A can be obtained by isolate | separating this by centrifugation, filtration, or combining these methods. Examples of the resin B include polyethylene oxide, polyethylene glycol, and polyvinyl alcohol, and these can be used alone or in combination.

<Average particle size of conductive particles>
As a standard of the average particle diameter of the conductive particles, it is less than 30 μm, particularly less than 10 μm.

<Volume resistivity of conductive particles>
The volume resistivity of the conductive particles is 10 ⁶ Ω · cm or less, particularly 10 ⁻³ Ω · cm or more and 10 ³ Ω · cm or less.

<Ratio of conductive particles to compound>
As a measure of the ratio between the conductive particles and the compound of the formula (1), a minimum amount of the compound is sufficient to cover the entire surface of the conductive particles.

<Method of coating conductive particles with compound>
Examples of the method for coating the conductive particles with the compound in the present invention include a wet method and a dry method.

Specifically, the wet method includes a method obtained by dissolving the compound of the present invention in a soluble solvent to form a solution, applying the solution to the surface of the conductive particles, and then drying the solvent. It is done.
More specifically, a method of spraying a solution of the compound while floating and flowing the conductive particles to form a coating layer of the compound on the surface of the conductive particles can be mentioned. Examples of such an apparatus include a Henschel mixer, a planetary mixer, a nauter mixer, and a multipurpose mixer.

As a dry method, a method in which compound particles and conductive particles are mixed and coated mechanically, a method in which conductive particles are coated with compound particles by mechanical impact force, a compound particle and conductive particles Examples thereof include a method such as a method of coating conductive particles by heating after mechanical mixing.
As an apparatus for mechanically mixing and coating compound particles and conductive particles, for example, Mechano Mill (Okada Seiko Co., Ltd.), Mechano Fusion System (Hosokawa Micron Co., Ltd.), Paint Conditioner (Red Devil Co.) Equipment can be used.
An apparatus such as a hybridizer (manufactured by Nara Machinery Co., Ltd.) can be used as an apparatus for coating conductive particles with compound particles by mechanical impact force.
Moreover, as an apparatus to heat-process, apparatuses, such as a spiracoater (made by Okada Seiko Co., Ltd.) and a fusing system (made by Nippon Numatic Co., Ltd.) can be used.

<Binder resin>
As the binder resin used for the surface layer, a known binder can be employed. Examples thereof include resins, natural rubber, vulcanized products thereof, and rubbers such as synthetic rubber.
As the resin, a resin such as a thermosetting resin or a thermoplastic resin can be used. Among these, fluorine resin, polyamide resin, acrylic resin, polyurethane resin, silicone resin, and butyral resin are more preferable.
Synthetic rubbers include ethylene-propylene-diene copolymer (EPDM), styrene-butadiene copolymer rubber (SBR), silicone rubber, urethane rubber, isoprene rubber (IR), butyl rubber, acrylonitrile-butadiene copolymer rubber (NBR). Chloroprene rubber (CR), acrylic rubber and epichlorohydrin rubber can be used.
These may be used alone, in combination of two or more, or may be a copolymer. Among these, as the binder resin used for the surface layer, it is preferable to use a resin from the viewpoint of high releasability without contaminating the photoreceptor or other members.

<Other particles added to the surface layer of the present invention>
The surface layer may contain insulating particles or the like as long as the effects of the present invention are not impaired.

The surface layer may contain a release agent in order to improve the surface releasability. By including a release agent in the surface layer, it is possible to prevent dirt from adhering to the surface of the charging member and improve the durability of the charging member. When the release agent is a liquid, it also acts as a leveling agent when forming the surface layer.
As such a release agent, a substance having physical properties such as low surface energy and slidability can be used, and solid and liquid materials can be used as its properties. Specifically, metal oxides such as molybdenum disulfide, tungsten disulfide, boron nitride, and lead monoxide can be given. In addition, oil- or solid-state compounds (mold release resin or powder thereof, a part of the polymer with a part having a release property) silicon or fluorine in the molecule, wax, higher fatty acid, salt thereof , Esters and other derivatives can also be used.

<Thickness of surface layer, other treatment>
The surface layer preferably has a thickness of 0.1 μm or more and 100 μm or less. More preferably, they are 1 micrometer or more and 50 micrometers or less.
The film thickness of the surface layer can be measured by cutting the charging roller section with a sharp blade and observing with an optical microscope or an electron microscope.

  The surface layer may be subjected to a surface treatment. Examples of the surface treatment include a surface processing treatment using UV or electron beam and a surface modification treatment for adhering and / or impregnating a compound on the surface.

<Surface roughness of charging member>
In the charging member of the present invention, it is more preferable that the surface ten-point average roughness Rzjis (μm) is 3 ≦ Rzjis ≦ 30, and the surface unevenness average interval Rsm (μm) is 15 ≦ Rsm ≦ 150. By setting the ten-point average surface roughness Rzjis and the uneven average interval Rsm of the charging member within these ranges, the contact state between the charging member and the electrophotographic photosensitive member can be made more stable. This is more preferable because it is easy to uniformly charge the photosensitive member.

A method for measuring the surface ten-point average roughness Rzjis and the surface unevenness average interval Rsm will be described below.
Measured according to JIS B0601-2001 surface roughness standards, and performed using a surface roughness measuring instrument “SE-3500” (trade name, manufactured by Kosaka Laboratory Ltd.). Rzjis is an average value obtained by measuring six charging members at random. Further, Rsm is a charging member randomly selected at six locations, and the uneven spacing at each of the 10 points is measured, and the average thereof is defined as Rsm at the measurement location.

<Formation of surface layer>
The surface layer can be formed by a coating method such as electrostatic spray coating or dipping coating. Or it can also form by adhere | attaching or coat | covering the sheet | seat shape or tube-shaped layer beforehand formed into a film thickness with the predetermined | prescribed film thickness. Alternatively, a method of curing and molding the material into a predetermined shape in the mold can also be used. Among these, it is preferable to apply a coating solution by a coating method to form a coating film (surface layer).

  When the surface layer is formed by a coating method, the solvent used in the coating solution may be any solvent that can dissolve the binder resin. Specifically, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide Sulphoxides, tetrahydrofuran, dioxane, ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, and aromatic compounds such as xylene, ligroin, chlorobenzene and dichlorobenzene. An aqueous coating solution can also be used.

<Volume resistivity of surface layer>
The volume resistivity of the surface layer is more preferably 1 × 10 ³ Ω · cm to 1 × 10 ¹⁵ Ω · cm in a 23 ° C./50% RH environment.
If the volume resistivity of the surface layer is smaller than this, if a pinhole occurs in the photoconductor, an excessive current flows through the pinhole, causing the applied voltage to drop, and the entire longitudinal direction of the pinhole part is strip-shaped. May appear in the image as a charging failure. On the other hand, if the volume resistivity is too large, it is difficult for current to flow through the charging roller, and the photosensitive member cannot be charged to a predetermined potential, and an adverse effect that an image does not have a desired density may occur.

  The volume resistivity of the surface layer is determined as follows. First, the surface layer is peeled off from the roller state and cut into strips of about 5 mm × 5 mm. Metal is vapor-deposited on both surfaces to produce an electrode and a guard electrode, and a measurement sample is obtained. Alternatively, it is applied on an aluminum sheet to form a surface layer coating film, and a metal for vapor deposition is deposited on the coating surface to obtain a measurement sample. A voltage of 200 V is applied to the obtained measurement sample using a microammeter (trade name: ADVANTEST R8340A ULTRA HIGH RESISTANCE METER, manufactured by Advantest Corporation). Then, the current after 30 seconds is measured and calculated from the film thickness and the electrode area.

<Conductive substrate>
The conductive substrate used in the charging member of the present invention is conductive and has a function of supporting a layer such as a surface layer provided thereon. Examples of the material include metals such as iron, copper, stainless steel, aluminum, and nickel, and alloys thereof.

<Elastic layer>
As a material used for the elastic layer, rubber or resin exemplified above as a component of the binder resin of the surface layer can be used.
Preferably, epichlorohydrin rubber, acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, urethane rubber, silicone rubber, SBS (styrene / butadiene / styrene / block copolymer), SEBS (styrene / ethylene butylene / styrene / block copolymer) Examples of the thermoplastic elastomer are as follows. Among these, polar adjustment is more preferable because resistance adjustment is easy. Among these, epichlorohydrin rubber and NBR can be mentioned. These have the advantage that resistance control and hardness control of the elastic layer can be performed more easily.

  In the epichlorohydrin rubber, the polymer itself has conductivity in the middle resistance region, and can exhibit good conductivity even if the amount of conductive particles added is small. Moreover, since the variation in electric resistance depending on the position can be reduced, it is suitably used as a polymer elastic body. Examples of the epichlorohydrin rubber include an epichlorohydrin homopolymer, an epichlorohydrin-ethylene oxide copolymer, an epichlorohydrin-allyl glycidyl ether copolymer, and an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Of these, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is particularly preferably used since it exhibits stable conductivity in a medium resistance region. The epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer can control conductivity and workability by arbitrarily adjusting the degree of polymerization and composition ratio.

  The elastic layer may be epichlorohydrin rubber alone, but it may contain epichlorohydrin rubber as a main component and other general rubber as necessary. Other common rubbers include ethylene / propylene rubber (EPM), ethylene-propylene-diene copolymer (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber, natural rubber, isoprene rubber, butadiene rubber. Styrene-butadiene rubber, urethane rubber, and silicone rubber. Further, a thermoplastic elastomer such as SBS (styrene / butadiene / styrene block copolymer) or SEBS (styrene / ethylene butylene / styrene block copolymer) may be contained. When said general rubber | gum is contained, it is more preferable that the content is 1 to 50 mass parts with respect to 100 mass parts of elastic layer materials.

The volume resistivity of the elastic layer is preferably 10 ² Ω · cm or more and 10 ¹⁰ Ω · cm or less as measured in a 23 ° C./50% RH environment. In order to adjust the volume resistivity, conductive particles such as carbon black, conductive metal oxide, alkali metal salt, and ammonium salt can be added as appropriate. When polar rubber is used for the elastic layer material, it is particularly preferable to use an ammonium salt.

  The elastic layer may contain additives such as insulating particles, softening oil, plasticizer, anti-aging agent and filler.

As a measure of the hardness of the elastic layer, the micro hardness (MD-1 type) is 70 ° or less, particularly 60 ° or less. This is to ensure a nip width between the charging member and the photosensitive member.
In addition, "micro hardness (MD-1 type)" is the hardness of the elastic layer measured using Asker micro rubber hardness meter MD-1 type (trade name, manufactured by Kobunshi Keiki Co., Ltd.). Specifically, the hardness meter is set to a value measured in a 10 N peak hold mode with respect to a charged layer left for 12 hours or more in an environment of normal temperature and normal humidity (23 ° C./55% RH).

  The volume resistivity of the elastic layer is measured as follows. Using the volume resistivity measurement sample obtained by forming all the materials used for the elastic layer into a sheet having a thickness of 1 mm and depositing metal on both sides to form electrodes and guard electrodes, The volume resistivity can be measured in the same manner as the rate measuring method.

  The elastic layer may be subjected to a surface treatment. Examples of the surface treatment include a surface processing treatment using UV or electron beam and a surface modification treatment for adhering and / or impregnating a compound on the surface.

  The elastic layer can be formed by adhering or covering a conductive substrate with a sheet-shaped or tube-shaped layer formed in advance to a predetermined film thickness. Further, it can also be formed by integrally extruding the conductive substrate and the elastic layer material using an extruder equipped with a cross head.

  The charging member of the present invention has a shape in which the central portion in the longitudinal direction is the thickest and becomes narrower toward both ends in the longitudinal direction from the viewpoint of making the nip width in the longitudinal direction of the charging member uniform with respect to the photoreceptor, so-called A crown shape is preferred. As an indication of the crown amount, the difference between the outer diameter of the central portion and the outer diameter at a position 90 mm away from the central portion is 30 μm or more and 200 μm or less.

<Intermediate layer>
One or more intermediate layers may be provided between the elastic layer and the surface layer. The volume resistivity of the intermediate layer is more preferably 10 ² Ω · cm to 10 ¹⁶ Ω · cm. In order to adjust the volume resistivity of the intermediate layer, substances such as the conductive particles and the insulating particles can be used.
In the intermediate layer of the present invention, materials exemplified in the elastic layer can be appropriately contained in addition to various substances contained in the surface layer. Similarly to the elastic layer, surface treatment using UV or electron beam or surface modification treatment for adhering and / or impregnating a compound on the surface may be performed.

<Electrophotographic device>
FIG. 4 shows a schematic configuration of an example of an electrophotographic apparatus provided with the charging member of the present invention.
The electrophotographic apparatus includes a photosensitive member, a charging device that charges the photosensitive member, a latent image forming device that performs exposure, a developing device that develops the toner image, a transfer device that transfers to a transfer material, and a cleaning that collects the transfer toner on the photosensitive member. The apparatus includes a device such as a fixing device for fixing a toner image.

The photoreceptor 4 is a rotary drum type having a photosensitive layer on a conductive substrate. The photoreceptor 4 is rotationally driven at a predetermined peripheral speed (process speed) in the direction of the arrow.
The charging device includes a contact-type charging roller 5 that is placed in contact with the photosensitive member 4 by being brought into contact with the photosensitive member 4 with a predetermined pressing force. The charging roller 5 is driven rotation that rotates in accordance with the rotation of the photosensitive member 4, and charges the photosensitive member 4 to a predetermined potential by applying a predetermined DC voltage from the charging power source 19 to the charging roller 5.
As the latent image forming apparatus 11 that forms an electrostatic latent image on the photoreceptor 4, for example, an exposure apparatus such as a laser beam scanner is used. An electrostatic latent image is formed on the photoreceptor 4 by performing exposure corresponding to image information on the uniformly charged photoreceptor 4.
The developing device has a developing roller 6 disposed close to or in contact with the photoreceptor 4. The toner electrostatically processed to the same polarity as the charged polarity of the photosensitive member 4 is developed by reversal, and the electrostatic latent image is visualized and developed into a toner image.
The transfer device has a contact-type transfer roller 8. The toner image is transferred from the photoreceptor 4 to a transfer material 7 such as plain paper (the transfer material is conveyed by a paper feed system having a conveying member).
The cleaning device includes a blade-type cleaning member 10 and a collection container, and after transferring, mechanically scrapes and collects transfer residual toner remaining on the photosensitive member 4.
Here, it is possible to omit the cleaning device by adopting a development simultaneous cleaning system in which the transfer device collects the transfer residual toner.
The fixing device 9 is composed of a member such as a heated roll, and fixes the transferred toner image on the transfer material 7 and discharges it outside the apparatus.

<Process cartridge>
It is also possible to use a process cartridge (FIG. 5) designed such that a photosensitive member, a charging device, a developing device, a cleaning device and the like are integrated and detachable from the main body of the electrophotographic apparatus.
That is, the charging member 5 is a process cartridge in which the charging member 5 is at least integrated with the photosensitive member 4 to be charged and is detachable from the main body of the electrophotographic apparatus, and the charging member is the charging member. The electrophotographic apparatus includes at least a process cartridge and an exposure apparatus, and the process cartridge is the process cartridge described above.
In the electrophotographic apparatus, it is preferable to charge only the direct current voltage to the charging member to charge the photosensitive member (charged member).

<Method for Measuring Molecular Weight of Compound of the Present Invention>
The molecular weight of the compound of the present invention was measured using a gel permeation chromatography (GPC) apparatus. The measured value was the number average molecular weight in terms of polystyrene as the molecular weight of the compound.

<Measuring method of average particle diameter of conductive particles>
The particle size of the conductive particles in the step before the inclusion in the surface layer was measured by a known method such as Coulter.
The method for measuring the particle size of the conductive particles already contained in the surface layer is to first observe the cross section of the surface layer with a TEM, and project the conductive particles from the cross-sectional image data of the conductive particles. The area is obtained, and then the diameter of a circle having an area equal to this area is obtained, and this is used as the particle diameter of the conductive particles. Similarly, the diameter of a circle having an area equal to this area was determined from the projected area of cross-sectional image data of another conductive particle, and the arithmetic average of the diameters of these circles was defined as the average particle diameter of the conductive particles.

<Method for measuring volume resistivity of conductive particles>
The volume resistivity of the conductive particles is measured in an environment of 23 ° C. and 55% Rh normal pressure. Measurement is performed with electrodes in which cylindrical electrodes made of stainless steel (made of SUS316) are arranged above and below a cylinder made of polytetrafluoroethylene (PTFE) having an inner diameter of 1 cm. The measurement sample and the electrode are measured after being left in the above environment for 12 hours or longer and acclimatized to the environment.
A SUS bottom electrode is placed at the bottom of a PTFE cylinder, about 2 g of conductive particles are placed so as not to be displaced, a SUS columnar electrode is placed from above, and sandwiched between the PTFE cylinder and the upper and lower electrodes. . The sample is allowed to stand for 1 minute or more with a pressure of 10 MPa applied. Thereafter, a voltage of 200 V is applied using a microammeter (trade name: ADVANTEST R8340A ULTRA HIGH RESISTANCE METER, manufactured by Advantest Corporation). Then, the current after 30 seconds is measured, and the volume resistivity is obtained by calculating from the distance between the electrode surfaces and the electrode area.

  Hereinafter, the present invention will be described in more detail with reference to specific examples, but the technical scope of the present invention is not limited thereto.

  In the compound having the unit represented by the formula (1), n is the number of units represented by the formula (1), and m is the number of units represented by the formula (4). .

[Production of compounds]
[Preparation of Compound 1] <Production Example D1>
As a solvent, 300 parts by mass of isopropyl alcohol was charged into a glass 1 liter flask equipped with a stirrer, a cooler, and a thermometer. Under stirring, the temperature was kept at 80 ° C., and the following compounds were added dropwise over 1 hour while passing nitrogen gas.
Compound represented by average molecular formula A: 90 parts by mass
Butyl acrylate: 78 parts by mass
Methyl methacrylate: 132 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
Furthermore, a polymerization reaction was performed at 80 ° C. for 6 hours. After a part of isopropyl alcohol was removed under reduced pressure, the remaining solution was put into a large amount of methanol, stirred and allowed to stand to obtain a precipitate. Further, the precipitate was dried under reduced pressure to obtain Compound 1.
The obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR. As a result, Compound 1 had α, β and γ units represented by the following formula (A-1). The number n of units represented by the formula (1) was 7, and the number m of units represented by the formula (4) was 192. The weight average molecular weight in terms of polystyrene (hereinafter referred to as PS) in terms of gel permeation chromatography (hereinafter referred to as GPC) of Compound 1 was about 30,000.

[Preparation of Compound 2] <Production Example D2>
A polymerization reaction was performed in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula A: 120 parts by mass
Ethyl acrylate: 90 parts by mass
Methyl methacrylate: 90 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 2 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol. When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 2 had α, β, and γ units represented by the following formula (A-2). The number n of units represented by the formula (1) was 6, and the number m of units represented by the formula (4) was 120. Moreover, the PS conversion weight average molecular weight by GPC of the compound 2 was about 20000.

[Preparation of Compound 3] <Production Example D3>
The polymerization reaction was carried out in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following and the solvent was changed to 300 parts by mass of ethanol.
Compound represented by average molecular formula A: 120 parts by mass
Butyl acrylate: 50 parts by mass
Methyl methacrylate: 50 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 3 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol. When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, Compound 3 had α, β and γ units represented by the following formula (A-3). The number n of units represented by the formula (1) was 6, and the number m of units represented by the formula (4) was 60. Moreover, the PS conversion weight average molecular weight by GPC of the compound 3 was about 15000.

[Preparation of Compound 4] <Production Example D4>
The mixture to be dropped was changed to the following, and the polymerization reaction was carried out in the same manner as in Production Example D1, except that the solvent was 100 parts by mass of ethanol and the reaction time was 10 hours.
Compound represented by average molecular formula A: 120 parts by mass
Styrene monomer: 20 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.5 part by mass
After the reaction, compound 4 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, compound 4 had α and β units represented by the following formula (A-4).
The number n of units represented by the formula (1) was 64, and the number m of units represented by the formula (4) was 135.
Moreover, PS conversion weight average molecular weight of GPC by GPC was about 100,000.

[Preparation of Compound 5] <Production Example D5>
The mixture to be dropped was changed to the following, and the polymerization reaction was carried out in the same manner as in Production Example D1, except that the solvent was 100 parts by mass of ethanol and the reaction time was 10 hours.
Compound represented by average molecular formula D: 130 parts by mass
Styrene monomer: 30 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.5 part by mass
After the reaction, compound 5 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, Compound 5 had α and β units represented by the following formula (A-5).
The number n of units represented by the formula (1) was 12, and the number m of units represented by the formula (4) was 177.
Moreover, PS conversion weight average molecular weight of GPC by GPC was about 100,000.

[Preparation of Compound 6] <Production Example D6>
The following was stirred at room temperature for 6 hours.
Ethanol: 100 parts by mass
Compound represented by average molecular formula L: 200 parts by mass
Methyl methacrylate: 50 parts by mass
The following compounds were added to this mixed solution to prepare a mixture to be dropped. Except this, it carried out similarly to manufacture example D1, and performed the polymerization reaction.
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.5 part by mass After the reaction, compound 6 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, compound 6 had α and β units represented by the following formula (A-6).
The number n of units represented by the formula (1) was 43, and the number m of units represented by the formula (4) was 1398.
Further, the weight average molecular weight in terms of PS by GPC of Compound 6 was about 700,000.

[Preparation of Compound 7] <Production Example D7>
A polymerization reaction was performed in the same manner as in Production Example D6, except that the substance added to the mixed solution was changed to the following.
Compound represented by average molecular formula P: 200 parts by mass
Methyl methacrylate: 50 parts by mass
After the reaction, compound 7 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, Compound 7 had α and β units represented by the following formula (A-7).
The number n of units represented by the formula (1) was 95, and the number m of units represented by the formula (4) was 998.
Moreover, PS conversion weight average molecular weight by GPC of the compound 7 was about 500,000.

[Preparation of Compound 8] <Production Example D8>
A polymerization reaction was performed in the same manner as in Production Example D4 except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula B: 100 parts by mass
Styrene monomer: 10 parts by mass
After the reaction, compound 8 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, Compound 8 had α and β units represented by the following formula (A-8).
The number n of units represented by the formula (1) was 112, and the number m of units represented by the formula (4) was 86.
Moreover, the PS conversion weight average molecular weight by GPC of the compound 8 was about 100,000.

[Preparation of Compound 9] <Production Example D9>
The substance added to the mixed solution was changed to the following, and the polymerization reaction was carried out in the same manner as in Production Example D6 except that the stirring time was 12 hours and the reaction time was 100 hours.
Compound represented by average molecular formula C: 100 parts by mass
Methyl methacrylate: 20 parts by mass
After the reaction, compound 9 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, compound 9 had α and β units represented by the following formula (A-9).
The number n of units represented by the formula (1) was 116, and the number m of units represented by the formula (4) was 250.
Moreover, PS conversion weight average molecular weight by GPC of the compound 9 was about 500,000.

[Preparation of Compound 10] <Production Example D10>
The substance added to the mixed solution was changed to the following, and the polymerization reaction was carried out in the same manner as in Production Example D9, except that the amount of initiator added was 1 part by mass.
Compound represented by average molecular formula N: 200 parts by mass
Methyl methacrylate: 20 parts by mass
Ethanol: 50 parts by mass
Acetone: 50 parts by mass
Toluene: 50 parts by mass
After the reaction, compound 10 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 10 had α and β units represented by the following formula (A-10).
The number n of units represented by the formula (1) was 159, and the number m of units represented by the formula (4) was 1634.
Moreover, PS conversion weight average molecular weight by GPC of the compound 10 was about 1800000.

[Preparation of Compound 11] <Production Example D11>
The mixture to be dropped was changed to the following, and the polymerization reaction was carried out in the same manner as in Production Example D1, except that the solvent was changed to 50 parts by mass of ethanol, 50 parts by mass of acetone, and 50 parts by mass of toluene.
Compound represented by average molecular formula O: 200 parts by mass
Methyl methacrylate: 50 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 11 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 11 had α and β units represented by the following formula (A-11).
The number n of units represented by the formula (1) was 2, and the number m of units represented by the formula (4) was 80.
Moreover, the PS conversion weight average molecular weight by GPC of the compound 11 was about 40000.

[Preparation of Compound 12] <Production Example D12>
A polymerization reaction was performed in the same manner as in Production Example D6, except that the substance added to the mixed solution was changed to the following.
Compound represented by average molecular formula M: 200 parts by mass
Methyl methacrylate: 50 parts by mass
Isopropyl alcohol: 50 parts by mass
Ethanol: 50 parts by mass
After the reaction, compound 12 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR and FT-IR, Compound 12 had α and β units represented by the following formula (A-12).
The number n of units represented by the formula (1) was 106, and the number m of units represented by the formula (4) was 1398.
Moreover, PS conversion weight average molecular weight by GPC of the compound 12 was about 700,000.

[Preparation of Compound 13] <Production Example D13>
A polymerization reaction was performed in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula H: 75 parts by mass
Methyl methacrylate: 120 parts by mass
Styrene monomer: 100 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 13 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 13 had α, β, and γ units represented by the following formula (A-13).
The number n of units represented by the formula (1) was 4, and the number m of units represented by the formula (4) was 290.
Moreover, PS conversion weight average molecular weight by GPC of the compound 13 was about 40000.

[Preparation of Compound 14] <Production Example D14>
A polymerization reaction was performed in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following and the solvent was changed to 100 parts by mass of ethanol.
Compound represented by average molecular formula L: 100 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 14 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding it to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 14 had an α unit represented by the following formula (A-14).
The number n of units represented by the formula (1) was 3, and the number m of units represented by the formula (4) was 0.
Moreover, the PS conversion weight average molecular weight by GPC of the compound 14 was about 39000.

[Preparation of Compound 15] <Production Example D15>
A polymerization reaction was performed in the same manner as in Production Example D11 except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula O: 100 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 15 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 15 had an α unit represented by the following formula (A-15).
The number n of units represented by the formula (1) was 2, and the number m of units represented by the formula (4) was 0.
Moreover, the PS conversion weight average molecular weight of GPC by GPC was about 30,000.

[Preparation of Compound 16] <Production Example D16>
A polymerization reaction was performed in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula ratio A: 90 parts by mass
Butyl acrylate: 78 parts by mass
Methyl methacrylate: 132 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 16 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, compound 16 had α, β, and γ units represented by the following formula (A-16).
Moreover, the PS conversion weight average molecular weight by GPC of the compound 16 was about 25000.

[Preparation of Compound 17] <Production Example D17>
A polymerization reaction was performed in the same manner as in Production Example D1, except that the mixture to be dropped was changed to the following.
Compound represented by average molecular formula ratio B: 100 parts by mass
Butyl acrylate: 90 parts by mass
Methyl methacrylate: 90 parts by mass
Radical polymerization initiator (α, α′-azobisisobutyronitrile): 0.3 part by mass
After the reaction, compound 17 was obtained by drying under reduced pressure at 150 ° C. and 10 mmHg without adding it to methanol.
When the obtained compound was analyzed by ²⁹ Si-NMR, ¹³ C-NMR, and FT-IR, Compound 17 had α, β, and γ units represented by the following formula (A-17).
Moreover, the PS conversion weight average molecular weight by GPC of the compound (17) was about 180,000.

[Preparation of conductive particles]
[Preparation of Conductive Particle 1]
To 7.0 kg of silica particles (average particle diameter 15 nm, volume resistivity 1.8 × 10 ¹² Ω · cm), 140 g of methyl hydrogen polysiloxane was added while operating the edge runner, and 588 N / cm (60 kg / cm ) Was mixed and stirred for 30 minutes. The stirring speed at this time was 22 rpm.
Into this, 7.0 kg of carbon black particles (particle diameter 20 nm, volume resistivity 1.0 × 10 ¹ Ω · cm, pH 6.0) was added over 10 minutes while operating the edge runner, and further 588 N / The mixture was stirred for 60 minutes with a linear load of cm (60 kg / cm). In this way, after carbon black is adhered to the surface of the coated silica particles in which methylhydrogenpolysiloxane is adhered to the surface of the silica particles, drying is performed at 80 ° C. for 60 minutes using a dryer. Obtained. The stirring speed at this time was 22 rpm. The obtained conductive particles 1 had an average particle diameter of 18 nm and a volume resistivity of 1.0 × 10 ² Ω · cm.

[Preparation of Conductive Particle 2]
A polyether ester amide resin (manufactured by Sanyo Chemical Industries, Ltd., trade name: Pelestat NC6321) 100 parts by mass, carbon black 20 parts by mass and a twin screw extruder were kneaded to obtain a mixture. 100 parts by mass of the obtained mixture and 200 parts by mass of polyethylene oxide (trade name R150, manufactured by Meisei Chemical Industry Co., Ltd.) were dry blended with a tumbler mixer and kneaded while heating at 260 ° C. with a twin screw extruder. A mixture was obtained. The obtained mixture was cooled to about 150 ° C. and then mixed with 10 liters of water as a dispersion medium to obtain a suspension of polyetheresteramide resin particles. This was centrifuged to separate the polyetheresteramide resin particles in which carbon black was dispersed, followed by drying by heating to obtain substantially spherical conductive particles 2 having an average particle diameter of 12 μm. The volume resistivity of the obtained conductive particles 2 was 1 × 10 ⁵ Ω · cm.
The polyethylene oxide used here is incompatible with the polyether ester amide and is water-soluble. Further, the polyether ester amide is insoluble in water.

[Preparation of Conductive Particle 3] <Production Example of Graphite Particle 1>
Β-Resin was extracted from coal tar pitch by solvent fractionation, and this was subjected to weighting treatment by hydrogenation. Subsequently, bulk mesophase pitch was obtained by removing solvent-soluble components with toluene. After this bulk mesophase pitch was mechanically pulverized, the temperature was raised to 270 ° C. in air at a temperature rising rate of 300 ° C./h, and an oxidation treatment was performed. This was classified so as to have an average particle size of 3.5 μm. Next, the pitch particles were heated to 3000 ° C. at a temperature increase rate of 1500 ° C./hr under a nitrogen atmosphere and held for 1 hour to be fired to obtain graphite particles 1 (the average particle size of the graphite particles 1 is 3 μm, volume resistivity was 1 × 10 ⁻² Ω · cm).

[Preparation of Conductive Particles 4] <Production Example of Graphite Particles 2>
Coal heavy oil was heat-treated, and the generated crude mesocarbon microbeads were centrifuged, washed with benzene, purified and dried. Subsequently, mechanical dispersion was performed with an atomizer mill to obtain mesocarbon microbeads. The mesocarbon microbeads were heated to 1200 ° C. at a temperature rising rate of 600 ° C./h in a nitrogen atmosphere, and then subjected to secondary dispersion in an atomizer mill. At this time, the average particle size was adjusted to about 15 μm. The particles were heated to 2800 ° C. at a heating rate of 1400 ° C./h in a nitrogen atmosphere and heat-treated at 2800 ° C. for 15 minutes to obtain graphite particles 2 (the average particle size of graphite particles 2 is 12 μm). The volume resistivity was 1 × 10 ⁻² Ω · cm).

[Preparation of Conductive Particle 5] <Production Example of Graphite Particle 3>
The phenol resin particles having an average particle diameter of 18 μm were heat-stabilized at 300 ° C. for 1 hour in an oxidizing atmosphere, heated to 1200 ° C./h to 2200 ° C., and heat-treated at 2200 ° C. for 10 minutes. Further, classification treatment was performed to obtain graphite particles 3 (the average particle diameter of the graphite particles 3 was 15 μm, and the volume resistivity was 1 × 10 ⁻² Ω · cm).

[Conductive particles 6]
Talker Black # 5500 (trade name, manufactured by Tokai Carbon Co., Ltd., primary particle size 25 nm, volume resistivity 1 × 10 ⁻² Ω · cm) was used as conductive particles 6.

[Conductive particles 7]
Denka black powder (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd., primary particle size 35 nm, volume resistivity 2 × 10 ⁻¹ Ω · cm) was used as the conductive particles 7.

[Conductive particles 8]
Mitsubishi # 3030 (trade name, manufactured by Mitsubishi Chemical Corporation, primary particle size 55 nm, volume resistivity 1 × 10 ⁰ Ω · cm) was defined as conductive particles 8.

[Conductive particles 9]
S-1 (trade name, manufactured by Gemco Co., Ltd., primary particle size 30 nm, volume resistivity 5 × 10 ⁵ Ω · cm) was designated as conductive particles 9.

[Conductive particles 10]
Passet CK (trade name, manufactured by Hakusuitec Co., Ltd., primary particle size 30 nm, volume resistivity 1 × 10 ⁴ Ω · cm) was defined as conductive particle 10.

[Conductive particles 11]
S-2000 (trade name, manufactured by Gemco Co., Ltd., primary particle size 30 nm, volume resistivity 5 × 10 ¹ Ω · cm) was used as the conductive particles 11.

[Conductive particles 12]
Passet GK (trade name, manufactured by Hakusuitec Co., Ltd., primary particle size 30 nm, volume resistivity 5 × 10 ¹ Ω · cm) was used as conductive particles 12.

[Conductive particles 13]
Copper particles (average particle size 15 μm, volume resistivity 1 × 10 ⁻³ Ω · cm) were used as conductive particles 13.

[Production of Conductive Composite Particles of the Present Invention]
[Preparation of Conductive Composite Particle 1] <Production Example P1>
Compound 1 obtained as described above was dissolved in cyclopentasiloxane to prepare a 40 wt% cyclopentasiloxane solution of compound 1.
100 parts by mass of the conductive particles 1 obtained as described above was charged into a multipurpose mixer (trade name, manufactured by Mitsui Mining Co., Ltd.) and rotated at 2000 rpm, while 250 parts by mass of a 40 wt% cyclopentasiloxane solution of Compound 1 was added. It was dripped.
This was dried at 80 ° C. for 30 minutes to obtain conductive composite particles 1 whose surfaces of the conductive particles 1 were coated with the compound 1.

[Preparation of Conductive Composite Particle 2] <Production Example P2>
Compound 1 obtained as described above was dissolved in isododecane to prepare a 40 wt% isododecane solution of compound 1.
As conductive particles, 100 parts by mass of conductive particles 6 was charged into a multipurpose mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), and 250 parts by mass of a 40 wt% isododecane solution of Compound 1 was added dropwise while rotating at 2000 rpm.
This was dried at 80 ° C. for 30 minutes to obtain conductive composite particles 2 in which the surfaces of the conductive particles 6 were coated with the compound 1.

[Preparation of Conductive Composite Particle 3] <Production Example P3>
Conductive composite particles 3 were obtained in the same manner as in Production Example P1, except that the conductive particles 3 were used as the conductive particles.

[Preparation of Conductive Composite Particle 4] <Production Example P4>
Conductive composite particles 4 were obtained in the same manner as in Production Example P1, except that conductive particles 7 were used as the conductive particles.

[Preparation of Conductive Composite Particle 5] <Production Example P5>
Conductive composite particles 5 were obtained in the same manner as in Production Example P1, except that the conductive particles 8 were used as the conductive particles.

[Preparation of Conductive Composite Particle 6] <Production Example P6>
Conductive composite particles 6 were obtained in the same manner as in Production Example P1, except that compound 2 was used as the compound and conductive particles 6 were used as the conductive particles.

[Preparation of Conductive Composite Particle 7] <Production Example P7>
Conductive composite particles 7 were obtained in the same manner as in Production Example P1, except that Compound 3 was used as the compound.

[Preparation of Conductive Composite Particle 8] <Production Example P8>
Compound 4 obtained as described above was made into fine powder of compound 4 by mechanical pulverization.
100 parts by mass of the fine particles of compound 4 are mixed with 100 parts by mass of the conductive particles 3 obtained as described above, and this mixture is charged into a mechanomill. Processed. In this way, conductive composite particles 8 in which the surfaces of the conductive particles 3 were coated with the compound 4 were obtained.

[Preparation of Conductive Composite Particles 9 to 38] <Production Examples P9 to P38>
Conductive composite particles 9 to 38 were obtained in the same manner as in Production Example P1, except that the compound, conductive particles, and addition amount thereof were changed as shown in Table 1. In addition, the addition amount of a compound shows the addition amount when the solid content of a compound is 100%.

[Preparation of Conductive Composite Particle 39] <Production Example P39>
The following compounds were mixed to prepare a methyl ethyl ketone mixed solution of compound 15 and acrylic resin.
Compound 15: 20 parts by mass
Acrylic resin (Delpet 60N (trade name), manufactured by Asahi Kasei Corporation): 20 parts by mass
Methyl ethyl ketone: 60 parts by mass
As a conductive particle, 100 parts by mass of the conductive particle 2 was charged into a multi-purpose mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), and 250 parts by mass of the mixed solution obtained above was dropped while rotating at 2000 rpm.
This was dried at 80 ° C. for 30 minutes to obtain conductive composite particles 39 in which the surfaces of the conductive particles 2 were coated with the substance containing the compound 15.

[Production of surface-treated titanium oxide particles] <Production Example T1>
1000 g of acicular rutile-type titanium oxide fine particles (average particle size 15 nm, length: width = 3: 1, volume resistivity 5.2 × 10 ¹⁰ Ωcm), 100 g of isobutyltrimethoxysilane as a surface treatment agent, and 3000 g of toluene as a solvent To prepare a slurry.
This slurry was mixed with a stirrer for 30 minutes, and then supplied to Viscomill in which 80% of the effective internal volume was filled with glass beads having an average particle diameter of 0.8 mm, and wet crushing was performed at a temperature of 35 ± 5 ° C. .
Toluene was removed from the slurry after wet pulverization by vacuum distillation (bath temperature: 110 ° C, product temperature: 30 ° C to 60 ° C, degree of vacuum: about 100 Torr) using a kneader, and the surface was kept at 120 ° C for 2 hours. The treating agent was baked. The fine particles subjected to baking treatment were cooled to room temperature and then pulverized using a pin mill to obtain surface-treated titanium oxide particles.

[Conductive substrate having an elastic layer]
A stainless steel round bar with a diameter of 6 mm and a length of 252.5 mm was coated with a thermosetting adhesive “Metalock U-20” (trade name, manufactured by Toyo Chemical Laboratory Co., Ltd.), and the dried one was used as a conductive substrate. used.
The following components were added to 100 parts by mass of epichlorohydrin rubber and kneaded for 10 minutes in a closed mixer adjusted to 50 ° C. to prepare a raw material compound.
Calcium carbonate: 60 parts by mass
Aliphatic polyester plasticizer: 8 parts by mass
Zinc stearate: 1 part by mass
2-mercaptobenzimidazole (MB) (anti-aging agent): 0.5 parts by mass
Zinc oxide: 2 parts by mass
Quaternary ammonium salt: 2 parts by mass
Carbon black (average particle diameter 100 nm, volume resistivity 0.1 Ωcm): 5 parts by mass
To this, 0.8 parts by mass of sulfur as a vulcanizing agent, 1 part by mass of dibenzothiazyl sulfite (DM) and 0.5 parts by mass of tetramethylthiuram monosulfide (TS) as vulcanization accelerators were heated to 20 ° C. The mixture was kneaded for 15 in a cooled two-roll mill to obtain an elastic layer compound.
Along with the conductive substrate, the elastic layer compound was extruded using an extruder with a crosshead and molded into a roller shape having an outer diameter of about 9 mm. Next, vulcanization and curing of the adhesive were performed in an electric oven at 160 ° C. for 1 hour. Thereafter, both ends of the elastic layer were cut off to make the length of the elastic layer 232 mm. Further, the surface is polished so that the outer diameter at the central portion in the longitudinal direction of the roller shape is 8.5 mm, an elastic layer is formed on the conductive substrate, and the conductive substrate with the elastic layer is formed. Got. The amount of crown of the conductive substrate with the elastic layer (the difference between the outer diameter at the center and the outer diameter at a position 90 mm away from the center) was 120 μm.

<Example 1>
[Preparation of coating solution for surface layer]
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution to adjust the solid content to 14% by mass.
The following components were added to 714.3 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.
Conductive composite particles 1: 45 parts by mass
Surface-treated titanium oxide particles: 20 parts by mass
Modified dimethyl silicone oil (* 1): 0.08 parts by mass
Block isocyanate mixture (* 2): 80.14 parts by mass
At this time, the blocked isocyanate mixture was such that the amount of isocyanate was “NCO / OH = 1.0”.
(* 1) is a modified dimethyl silicone oil “SH28PA” (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), and (* 2) is each of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). 7: 3 mixture of butanone oxime blocks.
200 g of the above mixed solution was placed in a glass bottle with an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 24 hours using a paint shaker disperser.
After the dispersion, 2.24 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added (corresponding to 10 parts by mass of polymethyl methacrylate resin particles with respect to 100 parts by mass of acrylic polyol solid content).
Thereafter, dispersion was performed for 1 hour, and the glass beads were removed to obtain a surface layer coating solution.

[Production of charging roller]
Using the surface layer coating solution, dipping coating was performed once on the conductive substrate having the elastic layer prepared above. After air drying at room temperature for 30 minutes or more, it was dried at 80 ° C. for 1 hour and further at 160 ° C. for 1 hour with a hot air circulating drier to obtain a charging roller having a surface layer formed on the elastic layer.
Here, the dipping coating is as follows. The immersion time was 9 seconds, the dipping coating lifting speed was an initial speed of 20 mm / s and a final speed of 2 mm / s, and the speed was changed linearly with respect to the time.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.

[Confirmation of presence of conductive composite particles in charging roller surface layer]
The surface layer of the charging roller was cut out with a sharp blade (for example, a razor) to produce a section of the surface layer cross section. Further, the surface layer slice was embedded in a resin and cut out with a microtome to obtain an observation sample. When observed with a TEM, the conductive particles present in the surface layer were covered with the compound 1. It was observed.

[Measurement of electrical resistance of charging roller]
The resistance of the charging roller was measured using the electrical resistance value measuring device shown in FIG.
First, the charging roller 5 is brought into contact with the cylindrical metal 32 (diameter 30 mm) by the bearing 33a and the bearing 33b so that the charging roller 5 is in parallel (FIG. 6A).
Here, the contact pressure was adjusted to 4.9 N at one end and 9.8 N in total at both ends by the pressing force of the spring.
Next, the charging roller 5 is driven to rotate in accordance with the cylindrical metal 32 that is driven and rotated at a peripheral speed of 45 mm / sec by a motor (not shown).
During the driven rotation, as shown in FIG. 6B, a DC voltage of −200 V is applied from the stabilized power source 34, and the current value flowing through the charging roller 5 is measured by the ammeter 35. The electric resistance of the charging roller 5 was calculated from the applied voltage and current value.
The charging roller 5 was left in an NN (normal temperature and normal humidity: 23 ° C./55% RH) environment for 24 hours or more, and then the electric resistance value was measured. The electric resistance value of the charging roller 5 was 9 × 10 ⁴ Ω.

[Evaluation of rustling image]
<Discharge idling acceleration test>
A color laser printer (LBP5400 (trade name)) manufactured by Canon Inc., which is an electrophotographic apparatus having the configuration shown in FIG. 4, was used. The process cartridge for the printer (for black) was used as the process cartridge having the configuration shown in FIG.
The attached charging roller was removed from the process cartridge, and the produced charging roller was set. Further, the charging roller 5 was brought into contact with the photosensitive member 4 with a pressing force by a spring of 4.9 N at one end and a total of 9.8 N at both ends (FIG. 7). Here, in a state where a DC voltage of −1000 V was applied to the charging roller 5, the photosensitive member 4 was rotated and rotated continuously for 20 hours, and the voltage was continuously applied.
After that, the electrophotographic apparatus (LBP5400 (trade name), manufactured by Canon Inc.) was modified as the electrophotographic apparatus shown in FIG. Using this electrophotographic apparatus, after outputting one image and stopping the rotation of the electrophotographic apparatus, the operation of restarting the image forming operation is repeated (intermittent durability at a printing rate of 1%). An output durability test was conducted.
The above test was performed in two environments of 23 ° C./50% RH (NN environment, hereinafter NN) and 15 ° C./10% RH (LL environment, hereinafter LL). During the endurance test, halftone images were output at the 1000th, 3000th, and 5000th time points, and the generation state of the rough image was evaluated from the images. The evaluation of the occurrence state was performed according to the following evaluation criteria.
<Evaluation criteria for rustling images>
Rank 1: Not generated.
Rank 2: It is a level that can hardly be confirmed with only slight occurrence.
Rank 3: Occurrence is recognized in a part of the image, but it is a level that causes no problem in practical use.
Rank 4: It occurs at the entire image and is a level at which the quality of the image is significantly reduced.

  Table 2 shows the evaluation results of the above-mentioned occurrence state. A rough image caused by the deterioration of the charging roller due to energization was not generated during the durability test, and a good image could be maintained.

[Confirmation of resistance increase rate]
Moreover, when the charging roller after the endurance test was taken out and the electric resistance value was measured, it was 1.02 × 10 ⁵ Ω. It was 14 times, and it was confirmed that there was very little deterioration by electricity supply.

<Example 2>
[Preparation of coating solution for surface layer]
A mixed solution of 25 parts by mass of the conductive composite particles 2 was prepared with respect to 100 parts by mass of Superflex 460 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is an aqueous urethane resin.
200 g of the above mixed solution was placed in a glass bottle having an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 2 hours using a paint shaker disperser.
After the dispersion, 2.24 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added (corresponding to 10 parts by mass of polymethyl methacrylate resin particles with respect to 100 parts by mass of acrylic polyol solid content).
Thereafter, dispersion was performed for 1 hour, and the glass beads were removed to obtain a surface layer coating solution.

[Production of charging roller]
Using the surface layer coating solution, after dipping and coating once on the conductive substrate having the elastic layer produced above, it is cured for 5 minutes at 80 ° C. in a hot air circulating dryer, and the surface layer is formed on the elastic layer. A formed charging roller was obtained.
Here, the dipping coating is as follows. The immersion time was 9 seconds, the dipping coating lifting speed was an initial speed of 20 mm / s and a final speed of 2 mm / s, and the speed was changed linearly with respect to the time.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.

[Confirmation of presence of conductive particles in charging roller surface layer]
The surface layer of the charging roller was cut out with a sharp blade (for example, a razor) to produce a section of the surface layer cross section. Furthermore, the surface layer slice was embedded in a resin and cut out with a microtome to obtain a sample for observation. When observed with a TEM, the conductive particles present in the surface layer were covered with compound 1. It was observed.

In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
In the charging roller of the present example, no rough image was generated during the durability test, and a good image could be maintained.

<Example 3>
[Preparation of coating solution for surface layer]
60 parts by mass of Superflex 460 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 40 parts by mass of Superflex 110 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is an aqueous urethane resin, conductive composite particles 3 30 parts by mass of was mixed to prepare a mixed solution.
200 g of the above mixed solution was placed in a glass bottle having an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 2 hours using a paint shaker disperser.
After the dispersion, 2.24 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added (corresponding to 10 parts by mass of polymethyl methacrylate resin particles with respect to 100 parts by mass of acrylic polyol solid content).
Thereafter, dispersion was performed for 1 hour, and the glass beads were removed to obtain a surface layer coating solution.

[Production of charging roller]
Using the surface layer coating solution, after dipping and coating once on the conductive substrate having the elastic layer produced above, it is cured for 5 minutes at 80 ° C. in a hot air circulating dryer, and the surface layer is formed on the elastic layer. A formed charging roller was obtained.
Here, the dipping coating is as follows. The immersion time was 9 seconds, the dipping coating lifting speed was an initial speed of 20 mm / s and a final speed of 2 mm / s, and the speed was changed linearly with respect to the time.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.

[Confirmation of presence of conductive particles in charging roller surface layer]
The surface layer of the charging roller was cut out with a sharp blade (for example, a razor) to produce a section of the surface layer cross section. Further, the surface layer slice was embedded in a resin and cut out with a microtome to obtain an observation sample. When observed with a TEM, the conductive particles present in the surface layer were covered with the compound 1. It was observed.

In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
In the charging roller of the present example, no rough image was generated during the durability evaluation, and a good image could be maintained.

<Examples 4 to 13>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
In the charging roller of the present example, no rough image was generated during the durability evaluation, and a good image could be maintained.

<Examples 14 to 17>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
An image level of rank 2 was generated by printing the LL 5000th sheet.

<Examples 18 to 25>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
An image level of rank 2 was generated on the LL 3000th sheet, the LL 5000th sheet, and the NN 5000th sheet.

<Examples 26 to 32>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
Rank 2 image levels were generated on the LL 3000th sheet, NN 3000th sheet, and NN 5000th sheet print, and rank 3 image levels were generated on the LL 5000th sheet print.

<Examples 33 to 35>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
The image level of rank 3 was generated by printing the LL 3000th sheet, the LL 5000th sheet, and the NN 5000th sheet.

<Example 36>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
The image level of rank 3 was generated by printing the LL 3000th sheet, the LL 5000th sheet, and the NN 5000th sheet.

<Comparative Examples 1-3>
A charging roller was produced in the same manner as in Example 3 except that the type of conductive composite particles and the amount added were changed as shown in Table 2.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
Rank 4 image level occurred.

<Comparative example 4>
A charging roller was produced in the same manner as in Example 3 except that only the carbon black was added without adding the conductive composite particles.
The thickness and surface roughness (Rzjis and RSm) of the surface layer of the obtained charging roller were measured. The results are shown in Table 2.
In the manufactured charging roller, measurement of the electric resistance value of the charging roller, evaluation of the roughness image, and confirmation of the rate of increase in resistance were performed in the same manner as in Example 1. The results are shown in Table 2.
Rank 4 image level occurred.

ＬＬ：１５℃／１０％ＲＨ環境
ＮＮ：２３℃／５０％ＲＨ環境

LL: 15 ° C / 10% RH environment NN: 23 ° C / 50% RH environment

DESCRIPTION OF SYMBOLS 1 Conductive base | substrate 2 Elastic layer 3 Surface layer 4 Photoconductor 5 Charging member (charging roller)
6 Developing roller 7 Transfer material 8 Transfer roller 9 Fixing device 10 Cleaning member 11 Latent image forming device 19 Power source 21 First intermediate layer 22 Second intermediate layer 32 Cylindrical metal 33a, 33b Bearing 34 Stabilizing power source 35 Ammeter

Claims (7)

A charging member having a conductive substrate and a surface layer,
The surface layer is
A binder resin,
A charging member comprising: conductive composite particles whose surfaces of conductive particles are coated with a compound having a unit represented by the following formula (1):

(In formula (1), R1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. G is a group having a structure represented by formula (2).)

(In the formula (2), A is an alkylene group having 2 to 10 carbon atoms, a phenylene group which may be substituted at least one selected from a methyl group and an ethyl group, and the following formulas (6) to (8): A represents 0 or 1. E1, E2 and E3 each independently represent a group represented by the following formula (3).)

(In the formulas (6) to (8), R8, R9 and R11 may each independently be substituted with at least one selected from an alkylene group having 1 to 10 carbon atoms, a methyl group and an ethyl group. In formula (8), R10 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 carbon atoms. And an aralkyl group, an allyl group or a halogen atom of 20 or less, d is an integer of 0 or more and 4 or less, and e is 0 or 1.)

(In Formula (3), k is 0 or 1. h is an integer of 0 or more and 3 or less.
Z1 is an alkylene group having 2 to 10 carbon atoms, a phenylene group which may be substituted at least one selected from a methyl group and an ethyl group, and a divalent group represented by the following formulas (15) to (17). A group selected from the group consisting of:
R3, R4, R6 and R7 each independently represent an alkyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group.
R5 is a group represented by the following formula (20) or the following formula (21) optionally substituted by at least one selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. .
X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, represented by the following formula (18). And a group selected from the group consisting of groups represented by the following formula (19). )

(In Formula (15) to Formula (17), R15, R16, and R17 may each independently be substituted with at least one selected from an alkylene group having 1 to 10 carbon atoms, a methyl group, and an ethyl group. (It is a phenylene group. P is an integer of 0 or more and 3 or less.)

(In formula (18), R18 is an alkylene group having 1 to 6 carbon atoms.)

(In the formula (19), r is 0 or 1, and s is an integer of 0 to 3. Z2 is at least one selected from an alkylene group having 2 to 10 carbon atoms, a methyl group, and an ethyl group. A group selected from the group consisting of an optionally substituted phenylene group and a divalent group represented by the above formulas (15) to (17) is shown.
R19, R20, R22 and R23 each independently represents an alkyl group having 1 to 5 carbon atoms or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group. R21 is a group represented by the following formula (20) or the following formula (21) optionally substituted by at least one selected from an alkoxy group having 1 to 10 carbon atoms, a methyl group and an ethyl group. .
X2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, represented by the above formula (18). And a group selected from the group consisting of groups represented by the above formula (19).
In the formula (3), when X is the following formula (19), the number of repeating groups represented by the formula (19) is 1 or more and 10 or less, and the most terminal formula (19) X2 therein is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an allyl group, a vinyl group which may be substituted at least one selected from a methyl group and an ethyl group, or the above formula (18) It is group shown by these. )

(In the formula (20), R24 is an alkylene group having 1 to 6 carbon atoms.)

(In the formula (21), R25, R26 and R27 each independently represent an optionally substituted alkyl group having 1 to 5 carbon atoms, or a phenyl group which may be substituted at least one selected from a methyl group and an ethyl group. ).   H in the formula (3) is 0, X is a group represented by the formula (19), and the number of repeating groups represented by the formula (19) is 1 or more and 3 or less, and The charging member according to claim 1, wherein r in the formula (19) is 0. The charging member according to claim 1, wherein the compound further has a unit represented by the following formula (4).

(In Formula (4), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. J is at least selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methyl group, and an ethyl group. On the other hand, it may be a substituted phenyl group, the following formula (9), the following formula (10), or a group represented by the following formula (11).

(In the formulas (9) to (10), R12 and R13 are each independently a phenyl group optionally substituted by at least one selected from an alkyl group having 1 to 6 carbon atoms, a methyl group and an ethyl group, And a group selected from the group consisting of groups represented by the formula (11), wherein R14 is at least one selected from an alkyl group having 1 to 4 carbon atoms, a methyl group, and an ethyl group. (It is an optionally substituted phenyl group. T is an integer of 1 to 3.)   The charging member according to claim 1, wherein an average particle diameter of the conductive particles is less than 10 μm. 5. The charging member according to claim 1, wherein a volume resistivity of the conductive particles is in a range of 10 ⁻³ Ω · cm to 10 ³ Ω · cm.   6. A process cartridge, wherein the charging member according to claim 1 is at least integrated with a member to be charged and is detachably attached to an electrophotographic apparatus main body.   An electrophotographic apparatus comprising at least the process cartridge and the exposure apparatus according to claim 6.

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