JP5952945B2 - Conductive member for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic conductive member used for an electrophotographic apparatus and a process cartridge.

  In an image forming apparatus employing an electrophotographic system, that is, an electrophotographic apparatus, a conductive member is used for various purposes, for example, a member such as a charging member, a developing member, or a transfer member. In the electrophotographic apparatus, the conductive layer of the charging roller, which is disposed in contact with the electrophotographic photosensitive member and charges the electrophotographic photosensitive member, is made of carbon black to adjust the conductivity of the conductive layer. Representative electronic conductive agents and ion conductive agents such as quaternary ammonium salt compounds are added. The ionic conductive agent is uniformly dispersed in the binder resin as compared with the electronic conductive agent. In Patent Document 1, an ionic conductive agent is selected as the conductive agent in order to reduce electric resistance unevenness due to uneven dispersion of the conductive agent in the binder resin.

  In Patent Document 2, a hydrophobic ionic liquid is used as an ionic conductive agent to improve the electrical resistance under low temperature and low humidity.

Japanese Patent Laid-Open No. 01-142569 JP 2003-202722 A

  A charging member having local unevenness in electrical resistance causes local discharge unevenness on the photoconductor, and consequently white or black blotch in an electrophotographic image, or streaky density unevenness. There is a case.

As described above, an ionic conductive agent is more advantageous than an electronic conductive agent as a conductive agent contained in the conductive layer in order to suppress uneven electrical resistance of the charging member. However, even a charging roller having a conductive layer made conductive with an ionic conductive agent may cause the above-described defects due to local discharge unevenness in an electrophotographic image. In particular, when the number of output electrophotographic images increases due to long-term use, or when image formation is performed in a low-temperature, low-humidity environment, the image may be deteriorated due to uneven electrical resistance of the charging member. There is a tendency for defects to increase.
Further, the ionic conductive agent may bleed (bleed) on the surface of the charging roller and adhere to the surface of the abutting electrophotographic photosensitive member.

  An object of the present invention is for electrophotography which can suppress the oozing of an ionic conductive agent and reduce the occurrence of image defects due to local discharge unevenness while ensuring the conductivity required for a charging roller. It is in providing a conductive member.

（式（５）中、Ｒ_１は、エチル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基またはｎ−デシル基を表す。）。
本発明によれば、導電性支持体および導電層を有する電子写真用の導電性部材であって、該導電層は、分子構造中にスルホン酸イオンを有するイオン導電性樹脂をバインダー樹脂として含み、かつ、下記式（６）または（７）で示されるキャリア分子を含むことを特徴とする導電性部材が提供される：

（式（６）及び式（７）中、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８はそれぞれ独立に、水素、または、炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。）。
本発明によれば、導電性支持体および導電層を有する電子写真用の導電性部材であって、該導電層は、分子構造中にスルホン酸イオンを有するイオン導電性樹脂をバインダー樹脂として含み、かつ、下記式（８）または（９）で示されるキャリア分子を含むことを特徴とする導電性部材が提供される：

（式（８）および式（９）中、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３およびＲ_１４はそれぞれ独立に、炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。）。
また、本発明によれば、導電性支持体および導電層を有する電子写真用の導電性部材であって、該導電層は、分子構造中にスルホン酸イオンを有するイオン導電性樹脂をバインダー樹脂として含み、かつ、下記式（１０）で示されるキャリア分子を含むことを特徴とする導電性部材が提供される：

（式（１０）中、Ｒ_１５、Ｒ_１６、Ｒ_１７、およびＲ_１８はそれぞれ独立に、水素または炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。）。 According to the present invention, there is provided a conductive member for electrophotography having a conductive support and a conductive layer, the conductive layer containing an ion conductive resin having a quaternary ammonium ion in the molecular structure as a binder resin. And the electroconductive member characterized by including the carrier molecule shown by following formula (5) is provided:

(Wherein (in 5), _{R 1} is. Representing the ethyl group, n- butyl group, sec- butyl group, tert- butyl group, n- hexyl, n- octyl or n- decyl).
According to the present invention, a conductive member for electrophotography having a conductive support and a conductive layer, the conductive layer containing an ion conductive resin having a sulfonate ion in a molecular structure as a binder resin, And the electroconductive member characterized by including the carrier molecule shown by following formula (6) or (7) is provided:

(In Formula (6) and Formula (7), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. And may contain a heteroatom).
According to the present invention, a conductive member for electrophotography having a conductive support and a conductive layer, the conductive layer containing an ion conductive resin having a sulfonate ion in a molecular structure as a binder resin, And the electroconductive member characterized by including the carrier molecule shown by following formula (8) or (9) is provided:

(In Formula (8) and Formula (9), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and includes a hetero atom. May be.)
According to the present invention, there is also provided an electrophotographic conductive member having a conductive support and a conductive layer, the conductive layer having an ion conductive resin having a sulfonate ion in a molecular structure as a binder resin. And a conductive member comprising a carrier molecule represented by the following formula (10):

(In Formula (10), R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may include a hetero atom).

  According to the present invention, there is provided a conductive member for electrophotography in which bleeding of an ionic conductive agent is suppressed and image defects caused by local uneven electrical resistance are hardly caused.

It is the schematic of the charging roller which is one form of the electrophotographic conductive member of this invention. It is the schematic of an electric current value measuring machine. It is a schematic diagram of the conductive layer which concerns on this invention. It is explanatory drawing of the electrophotographic apparatus which concerns on this invention. It is explanatory drawing of the process cartridge which concerns on this invention.

The present inventors presume the cause of local discharge unevenness in a charging roller having a conductive layer made conductive with an ionic conductive agent as follows.
That is, the carrier molecules derived from the ionic conductive agent contained in the conductive layer have different moving speeds in the conductive layer for each type.

上記式（１）中、ρは電気抵抗率、ｑはキャリアの電荷、ｎはキャリア密度、μはキャリア移動度を表す。上記式（１）から明らかなように、帯電ローラ中で局所的にμが小さいキャリア分子が局在した領域や、μが大きなキャリア分子が局在した領域が存在すると、帯電ローラの電気抵抗ムラに関与することが予想される。
特に、μが大きなキャリア分子が局在した領域は、局所的に電気抵抗が下がるため、異常放電による白斑点画像が発生しやすい。 Here, the moving speed of the carrier molecule can be expressed by the carrier mobility μ, and the relationship between the carrier mobility μ and the electrical resistivity ρ can be expressed by the following formula (1).

In the above formula (1), ρ represents electrical resistivity, q represents carrier charge, n represents carrier density, and μ represents carrier mobility. As is apparent from the above formula (1), if there is a region where carrier molecules having a small μ are localized in a charging roller or a region where carrier molecules having a large μ are localized, the electric resistance of the charging roller is uneven. Is expected to be involved.
In particular, in a region where carrier molecules having a large μ are localized, the electrical resistance is locally reduced, and thus a white spot image due to abnormal discharge is likely to occur.

  Here, the present inventors reduced the moving speed of the carrier molecules moving in the conductive layer in order to reduce the unevenness of the moving speed of the carrier molecules when a DC voltage is applied to the charging roller. Tried. Specifically, the effect of reducing the electric resistance unevenness on the charging roller when μ of the carrier molecules existing in the conductive layer was reduced was examined.

As a result, the charging roller having a conductive layer made conductive using an ionic conductive agent having carrier molecules having a small μ is less likely to cause uneven electrical resistance even when a DC voltage is applied for a long time. As a result, it has been found that the occurrence of image defects due to uneven discharge can also be reduced.
Since the electroconductive member which concerns on this invention has couple | bonded the ionic conductive agent with the binder resin through the covalent bond, the component which contributes to ionic conduction can be limited to either a cation or an anion. Furthermore, by being bonded to the binder resin, even when a DC voltage is applied to the charging roller for a long time, the oozing of the ionic conductive agent from the conductive layer can be reduced as much as possible.

  Hereinafter, the present invention will be described in more detail. Hereinafter, the details of the charging member will be described as the electrophotographic conductive member, but the present invention is not limited to the charging member. FIG. 1 shows a schematic view of the charging member of the present invention.

  As shown in FIG. 1A, the charging member according to the present invention can include a cored bar 11 as a conductive support and an elastic layer 12 provided on the outer periphery thereof. The elastic layer 12 is a conductive layer and is made of the ion conductive resin according to the present invention. As shown in FIG. 1B, a surface layer 13 may be formed on the surface of the elastic layer 12. In this case, at least one of the elastic layer 12 or the surface layer 13 is a conductive layer and is made of the ion conductive resin according to the present invention. As shown in FIG. 1C, a three-layer structure in which an intermediate layer 14 is disposed between the elastic layer 12 and the surface layer 13 or a multilayer structure in which a plurality of intermediate layers 14 are disposed may be employed. In this case, at least one of the layers is a conductive layer, and the conductive layer is made of the ion conductive resin according to the present invention.

<Conductive support>
As the conductive support, it can be appropriately selected from those known in the field of electrophotographic conductive members.

<Conductive layer>
The conductive layer according to the present invention contains, as a binder resin, an ion conductive resin having either one or both ion exchange groups selected from quaternary ammonium ions and sulfonate ions in the molecular structure, and a specific resin. Contains carrier molecules. The ion exchange group according to the present invention is covalently bonded to the resin and is ion dissociated.
FIG. 3 is a schematic cross-sectional view of one embodiment of the conductive layer according to the present invention. The conductive layer 31 includes an ion conductive resin 32 formed by covalently bonding a quaternary ammonium ion to a polymer chain as an ion exchange group. Is included as a binder resin. The conductive layer 31 is, as free carrier molecule contains a career molecule 33.

(1) Carrier molecule The carrier molecule is originally a counter ion of the above-described ion exchange group. In the conductive layer, it is considered that at least some of the carrier molecules are dissociated from the above-described ion exchange groups and exist in a free state. Then, by applying a DC voltage to the conductive member, the free carrier molecules move through the binder resin to achieve ionic conduction.

As described above, by using carrier molecules having a small μ, it is possible to reduce the occurrence of uneven electrical resistance on the charging member when a voltage is applied to the charging member for a long time. On the other hand, carrier molecules having a small μ are relatively disadvantageous compared to carrier molecules having a large μ in conducting the conductive layer. Therefore, the present inventors have repeatedly investigated carrier molecules that can achieve both a high level of conductivity of the conductive layer and a reduction in the occurrence of uneven electrical resistance on the conductive member. As a result, it has been found that when the binder resin has quaternary ammonium ions in the molecule, the conductive layer preferably contains at least one selected from carrier molecules represented by the following formula ( 5). Moreover, when binder resin contains a sulfonate ion in a molecule | numerator, it discovered that it was preferable that a conductive layer contains at least 1 selected from the carrier molecule shown by following formula (6)-(10). .

In formula (5), R ₁ represents an ethyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-octyl group, or an n-decyl group . Specific examples of the carrier molecule represented by the above formula (5) are given below. Methyl sulfonate, ethyl sulfonate, n-butyl sulfonate, sec-butyl sulfonate, tert-butyl sulfonate, n-hexyl sulfonate, n-octyl sulfonate, n-decyl sulfonate, and the like.

式（６）中、Ｒ_２、Ｒ_３およびＲ_４はそれぞれ独立に、水素または炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。

In formula (6), R ₂ , R ₃ and R ₄ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms and may contain a hetero atom.

Specific examples of the compound represented by formula (6) are given below.
1-methylimidazolium, 1-ethylimidazolium, 1-butylimidazolium, 1-octylimidazolium, 1-decylimidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- Propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-octyl-3 methylimidazolium, 1-decyl-3-methylimidazolium, 1, 3 -Diethylimidazolium, 1-propyl-3-ethylimidazolium, 1-butyl-3-ethylimidazolium, 1-hexyl-3-ethylimidazolium, 1-octyl-3 ethylimidazolium, 1-decyl-3- Ethyl imidazolium, 1,2,3-trimethylimidazolium, 1-d 2,3-dimethylimidazolium, 1-propyl-2,3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1-octyl- 2,3-dimethylimidazolium, 1-decyl-2,3-dimethylimidazolium, 1-butyl-3-ethylimidazolium and the like.

式（７）中、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８はそれぞれ独立に、水素または炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。

In formula (7), R ₅ , R ₆ , R ₇ and R ₈ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms and may contain a hetero atom.

Specific examples of the compound represented by the formula (7) are given below.
N-methylpyridinium, N-ethylpyridinium, N-butylpyridinium, N-hexylpyridinium, N-octylpyridinium, N-decylpyridinium, N-methyl-3-methylpyridinium, N-ethyl-3-methylpyridinium, N- Butyl-3-methylpyridinium, N-hexyl-3-methylpyridinium, N-octyl-3-methylpyridinium, N-decyl-3-methylpyridinium, N-methyl-4-methylpyridinium, N-ethyl-4-methyl Pyridinium, N-butyl-4-methylpyridinium, N-hexyl-4-methylpyridinium, N-octyl-4-methylpyridinium, N-decyl-4-methylpyridinium, N-methyl-3,4-dimethylpyridinium, N -Ethyl-3,4-dimethylpyridini N-butyl-3,4-dimethylpyridinium, N-hexyl-3,4-dimethylpyridinium, N-octyl-3,4-dimethylpyridinium, N-decyl-3,4-dimethylpyridinium, N-methyl- 3,5-dimethylpyridinium, N-ethyl-3,5-dimethylpyridinium, N-butyl-3,5-dimethylpyridinium, N-hexyl-3,5-dimethylpyridinium, N-octyl-3,5-dimethylpyridinium N-decyl-3,5-dimethylpyridinium and the like.

式（８）中、Ｒ_９およびＲ_１０はそれぞれ独立に、水素または炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。

In formula (8), R ₉ and R ₁₀ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may contain a hetero atom.

Specific examples of the compound represented by the formula (8) are given below.
1,1-dimethylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-hexyl-1-methylpyrrolidinium, 1-octyl-1-methylpyrrole Dinium, 1-decyl-1-methylpyrrolidinium, 1,1-diethylpyrrolidinium, 1-butyl-1-ethylpyrrolidinium, 1-hexyl-1-ethylpyrrolidinium, 1-octyl-1 -Ethylpyrrolidinium, 1-decyl-1-ethylpyrrolidinium, 1,1-dibutylpyrrolidinium, and the like.

式（９）中、Ｒ_１１、Ｒ_１２、Ｒ_１３およびＲ_１４はそれぞれ独立に、炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。

In formula (9), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrocarbon group having 1 to 10 carbon atoms and may contain a hetero atom.

Specific examples of the compound represented by the formula (9) are given below.
Tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetradecylammonium, methyltriethylammonium, methyltributylammonium, methyltrioctylammonium, methyltridecylammonium, ethyltrimethylammonium, butyl Trimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, phenyltrimethylammonium, cyclohexyltrimethylammonium, diallyldimethylammonium, (2-chloroethyl) trimethylammonium, (2-hydroxyethyl) trimethylammonium and the like.

式（１０）中、Ｒ_１５、Ｒ_１６、Ｒ_１７およびＲ_１８はそれぞれ独立に、炭素数１乃至１０の炭化水素基を表し、ヘテロ原子を含んでもよい。

In formula (10), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represent a hydrocarbon group having 1 to 10 carbon atoms and may contain a hetero atom.

Specific examples of the compound represented by the formula (10) are given below.
Tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium, tetradecylphosphonium, methyltriethylphosphonium, methyltributylphosphonium, methyltrioctylphosphonium, methyltridecylphosphonium, ethyltrimethylphosphonium, butyl Trimethylphosphonium, hexyltrimethylphosphonium, octyltrimethylphosphonium, decyltrimethylphosphonium, phenyltrimethylphosphonium, cyclohexyltrimethylphosphonium, (2-chloroethyl) trimethylphosphonium, (2-hydroxyethyl) trimethylphosphonium, and the like.

  In addition, you may use multiple types of the above-mentioned carrier molecule.

The carrier molecule having the structure represented by the formulas ( 5 ) to (10) is characterized by a very large molecular size as compared with general carrier molecules such as protons and halogen ions. Therefore, it is considered that the ion mobility μ is small and the object of the present invention can be achieved.

For example, in the carrier molecule represented by the formula (9), when R _{11 to} R ₁₄ are hydrocarbon groups having 11 or more carbon atoms, the charging member is applied when a DC voltage is applied for a long time. It was recognized that the electrical resistance of the glass tends to increase. This is considered to be caused by the entanglement between the binder resin and R _{11 to} R ₁₄ . It is presumed that the electrical resistance has increased as a result of restricting the movement of carrier molecules due to the entanglement with the binder resin.

For the reasons described above, carrier molecules having a large molecular size and a structure that hardly causes entanglement with the binder resin are preferred in the present invention. Among the carrier molecules, in particular , the formulas (6) to (8) The carrier molecules are preferred.

  Further, since the carrier molecule according to the present invention has a high affinity with the binder resin, it is preferable in that the carrier molecule can be uniformly dispersed with the binder resin and the electrical resistance unevenness due to the dispersion unevenness can be further reduced.

  Furthermore, since the carrier molecule according to the present invention exhibits the properties of an ionic liquid, it exists as a liquid even in a state where the amount of water is small, and can move through the binder resin. Furthermore, it is suitable also in the point which can improve the fall of electrical resistance in a low-humidity environment. Here, the ionic liquid refers to a molten salt having a melting point of 100 degrees or less.

By the way, the conductive layer according to the present invention may contain carrier molecules that contribute to ionic conduction other than the carrier molecules represented by the above formulas ( 5 ) to (10). However, when there are a plurality of types of carrier molecules having different carrier mobilities μ in the conductive layer, uneven electrical resistance tends to occur in the conductive layer. Therefore, the proportion of the carrier molecules represented by the above formulas ( 5 ) to (10) with respect to the carrier molecules contributing to ion transmission contained in the conductive layer according to the present invention is 50 mol% or more and 100 mol%. In particular, it is particularly preferably 70 mol% or more and 100 mol% or less.

  The presence and quantification of the carrier molecule according to the present invention in the conductive layer can be verified by extracting the carrier molecule using an ion exchange reaction. The ion conductive resin is stirred in a dilute aqueous solution of hydrochloric acid or sodium hydroxide, and carrier molecules in the ion conductive resin are extracted into the aqueous solution. The aqueous solution after extraction is dried, the extract is collected, and then mass spectrometry is performed with a time-of-flight mass spectrometer (TOF-MS), whereby carrier molecules can be identified and quantified. In addition, since the carrier molecule in an extract is a cation or an anion molecule, even when the molecular weight of a carrier molecule is high, it can analyze without decomposing a carrier molecule in TOF-MS measurement. Furthermore, elemental analysis is performed by inductively coupled plasma (ICP) emission analysis of the extract, and combined with the results of mass spectrometry, it becomes easier to identify and quantify carrier molecules.

(2) Binder resin As the binder resin according to the present invention, an ion conductive resin having any one or both selected from a quaternary ammonium group and a sulfonic acid group in the molecular structure is used.
And as an ion conductive resin which concerns on this invention, it is preferable to use what does not have the carrier molecule which contributes to ion conduction other than the carrier molecule based on this invention as a counter ion of a quaternary ammonium group. This is to prevent generation of large electric resistance unevenness in the conductive layer due to the presence of carrier molecules having different carrier mobility in the conductive layer.
For example, it is known that an ion conductive rubber typified by epichlorohydrin rubber has a low electrical resistance when vulcanized. This is because the vulcanization accelerator used at the time of vulcanization forms a salt with chlorine released by heating, sulfur of additive, sulfur released from vulcanization accelerator, etc., and expresses the function as an ionic conductive agent It is thought to do. In other words, as a result of vulcanization of epichlorohydrin rubber, chlorine ions, sulfur ions, ions derived from vulcanization accelerators, and the like are generated as carrier molecules.

  For the reasons described above, the ion conductive resin according to the present invention is preferably a resin that is difficult to produce a compound exhibiting ionic conductivity by polymerization or heating. Examples of the resin that satisfies the above conditions include an epoxy resin having an ion exchange group, a urethane resin, an ester resin, an amide resin, an imide resin, an amideimide resin, a phenol resin, a vinyl resin, a silicone resin, and a fluorine resin.

  Since the resin group described above can produce a resin only with a monomer component or polymer component as a raw material and an ionic conductive agent that reacts with the resin and binds to the resin via a covalent bond, the types of carrier molecules that contribute to ionic conduction Can be reduced as much as possible. In the present invention, it is particularly preferable to use a phenol resin among the resin group. Since the main chain skeleton of the resin is formed of an aromatic ring, the phenol resin is less likely to be entangled with the carrier molecule and is suitable for the purpose of the present invention.

  From the viewpoint of ionic conductivity, the ionic conductive resin preferably has an ethylene oxide unit in the molecular structure. Content of an ethylene oxide unit can be set suitably. However, since the ethylene oxide unit content correlates with the moisture content in the ion conductive resin, it tends to dominate the temperature / humidity dependence of the electrical resistance value of the ion conductive resin. For the reasons as described above, it is preferable that the content of the ethylene oxide unit can be adjusted to a range of 30 wt% to 80 wt%. More specifically, it is preferably 40 wt% or more and 60 wt% or less. When the content is 40 wt% or more, it is possible to prevent an increase in electrical resistance in a low temperature / low humidity environment. When the content is 60 wt% or less, it is possible to prevent a decrease in electrical resistance under a high temperature / high humidity environment. In addition, content of an ethylene oxide unit is computable as a weight ratio of the ethylene oxide unit in the binder resin as a raw material.

<Method for producing ion conductive resin>
The ion conductive resin according to the present invention can be produced by, for example, the following method using (1) an ion conductive agent as a raw material and (2) a polymer or monomer as a raw material for a binder resin.

(1-1) Preparation of an ionic conductive agent as a raw material;
As a raw material for the ion conductive resin, an ion conductive agent having a portion capable of chemically reacting with the binder resin and having either a quaternary ammonium group or a sulfonic acid group is prepared.
Here, examples of the moiety capable of chemically reacting with the binder resin include a binding site of a halogen atom (fluorine, chlorine, bromine and iodine atom) and a reactive functional group. Specific examples of reactive functional groups include carboxyl groups, acid groups such as acid anhydrides, hydroxyl groups, amino groups, mercapto groups, alkoxy groups, vinyl groups, glycidyl groups, epoxy groups, nitrile groups, carbamoyl groups, and the like. .

(1-2) introduction of carrier molecules into the ionic conductive agent;
Next, the carrier molecule according to the present invention is introduced into the ionic conductive agent prepared in (1-1) above. Specifically, by carrying out an ion exchange reaction between the salt of the carrier molecule according to the present invention and the quaternary ammonium group or sulfonic acid group of the ionic conductive agent prepared in (1-1) above, An ionic conductive agent into which carrier molecules according to the invention are introduced can be obtained.
For example, the case where the ionic conductive agent prepared in (1-1) is glycidyltrimethylammonium chloride will be described as an example. First, lithium bis (trifluoromethanesulfonyl) imide is prepared as the carrier molecule salt. Then, each of the ion conductive agent and the salt of the carrier molecule is dissolved in purified water. Next, each aqueous solution is mixed and stirred to cause an ion exchange reaction, whereby chlorine ions having high ion exchange properties are replaced with bis (trifluoromethanesulfonyl) imide ions.
In this case, since the produced glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide is a hydrophobic ionic liquid, water-soluble lithium chloride as a by-product can be easily removed. Similarly, since all of the ionic conductive agents composed of carrier molecules according to the present invention have ionic liquid characteristics, even when the reactive ionic conductive agent obtained by the above-described method is hydrophilic, chloroform, dichloromethane, dichloroethane, By-products can be easily removed by selecting a solvent such as methyl isobutyl ketone.

(2) reaction of the ionic conductive agent with the raw material polymer or raw material monomer of the binder resin;
The polymer or monomer as the raw material of the binder resin can be used without any particular limitation as long as it reacts with the reactive functional group contained in the ionic conductive agent. A specific example is given. Polyglycidyl compound, polyamine compound, polycarboxy compound, polyisocyanate compound, polyhydric alcohol compound, polyisocyanate compound, phenol compound, vinyl compound, etc., compound having two or more reactive functional groups, compound having polymerizable property alone etc.
As an example of the ionic conductive agent according to (1-2) above, an ionic conductive agent obtained by ion exchange of the chloride ion of glycidyltrimethylammonium chloride with cyclohexafluoropropane-1,3-bis (sulfonyl) imide is used. A method for synthesizing the ion conductive resin according to the present invention will be described.
Polypropylene glycol diglycidyl ether and polypropylene glycol bis (2-aminopropyl ether) are prepared as raw materials for the binder resin.
Then, a coating material is prepared by dissolving the ionic conductive agent and the raw material polymer in a solvent such as isopropyl alcohol.
By heating the coating film of this paint at a temperature of 90 to 200 ° C., an ionic conductive resin in which a glycidyl group and an amino group react and a quaternary ammonium having a carrier molecule according to the present invention as a counter ion is bonded. can get.
The addition amount of the ionic conductive agent according to the present invention can be appropriately set, and the ionic conductive agent is contained in a proportion of 0.5% by mass or more and 20% by mass or less with respect to the polymer or monomer as the raw material of the binder resin. It is preferable to mix. As a result, it is possible to obtain an ion conductive resin that is excellent in conductivity and suitable for forming a conductive layer that is less likely to cause uneven electrical resistance.
The method for synthesizing the ion conductive resin according to the present invention is not limited to the method described above. For example, after synthesizing an ion conductive resin in which an ionic conductive agent having protons or halogen ions as carrier molecules is introduced, the ions according to the present invention are ion-exchanged with the carrier molecules according to the present invention. A method of synthesizing a conductive resin can also be employed.

<Other ingredients>
In the ion conductive resin, a filler, a softening agent, a processing aid, a tackifier, an anti-tacking agent, a dispersant, which are generally used as a resin compounding agent, as long as the effects of the present invention are not impaired. A foaming agent or the like can be added.

<Conductive roller>
The conductive member according to the present invention can be suitably used, for example, as a charging member for contacting a member to be charged such as a photoconductor to charge the member to be charged. In addition, in a process cartridge having an image carrier and a charging member that contacts the image carrier and charges the image carrier by applying a voltage, the process cartridge is configured to be detachable from the image forming apparatus main body. As the charging member, the conductive member according to the present invention can be suitably used.
In addition to the charging member such as a charging roller, the ion conductive resin of the present invention can be used as a developing member, a transfer member, a charge eliminating member, or a conveying member such as a paper feed roller.

  FIG. 1 is a schematic view showing the form of a charging roller which is a kind of electrophotographic conductive member of the present invention. As shown in FIG. 1A, the charging roller may have a single-layer structure including a cored bar 11 and an elastic layer 12 provided on the outer periphery thereof. As shown in FIG. A two-layer configuration in which the surface layer 13 is disposed outside the elastic layer 12 may be employed. Furthermore, as shown in FIG. 1C, a multilayer configuration in which several intermediate layers 14 and adhesive layers are arranged between the elastic layer 12 and the surface layer 13 may be employed. At least one of the elastic layer 12, the surface layer 13, and the intermediate layer 14 in FIG. 1 is a conductive layer, and the ion conductive resin according to the present invention may be used for any layer.

  Furthermore, since it is near the surface of the charging roller that is involved in the discharge as the charging roller, it is preferable to use the ion conductive resin of the present invention in the vicinity of the surface layer that can improve discharge unevenness. In this case, it is not always necessary to use the ion conductive resin of the present invention for the outermost layer, and as long as it does not affect discharge unevenness, the outermost layer is subjected to a non-adhesive treatment for the purpose of preventing adhesion of toner and external additives. It doesn't matter. As the non-adhesive treatment of the outermost layer, a method of curing the surface by irradiating the surface of the charging roller with energy rays such as electron beam, ultraviolet ray, X-ray and microwave, and making the surface non-adhesive, acrylic resin, polyurethane, polyamide, Non-adhesive resins such as polyester, polyolefin, and silicone resin may be formed as the outermost surface layer.

The electric resistance of the conductive member according to the present invention is 1 × 10 ³ Ω · cm or more and 1 × 10 ⁹ Ω · cm or less, but the electric resistance is 1 × 10 ⁵ Ω · cm or more and 1 × 10 ^8. Effective when Ω · cm or less. The occurrence of abnormal discharge due to leakage can be suppressed by setting it to 1 × 10 ⁵ Ω · cm or more, and the occurrence of image defects due to insufficient electrical resistance can be suppressed by setting it to 1 × 10 ⁸ Ω · cm or less.

  When the ion conductive resin according to the present invention is used as the surface layer 13 of the elastic layer 12 as shown in FIG. 1B, the rubber component forming the elastic layer 12 is not particularly limited, Known rubbers can be used in the field of electrophotographic conductive members. Specifically, epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene copolymer hydrogenated product, acrylic Examples thereof include rubber and urethane rubber.

  When the ion conductive resin according to the present invention is used as the elastic layer 12 or an intermediate layer between the elastic layer 12 and the surface layer 13, the surface layer 13 can use a resin known in the field of electrophotographic conductive members. . Specific examples include acrylic resin, polyurethane, polyamide, polyester, polyolefin, and silicone resin. For the resin forming the surface layer, the surface of the particles may be coated with conductive oxides such as carbon black, graphite, and tin oxide, metals such as copper and silver, oxides and metals, if necessary. Alternatively, an ion conductive agent having ion exchange performance such as conductive particles and quaternary ammonium salts imparted with conductivity may be used.

[Electrophotographic equipment]
The electrophotographic apparatus according to the present invention only needs to have the electrophotographic conductive member according to the present invention, and an example of the schematic configuration is shown in FIG. An electrophotographic photosensitive member 44 (hereinafter also referred to as “photosensitive member”), a process cartridge in which a charging device having a charging member 45 made of a conductive member according to the present invention is integrated, a latent image forming device (not shown) And a transfer device for transferring the toner image to a transfer material 47 such as paper. Further, it includes a cleaning device 48 that collects toner remaining on the photoconductor after the toner image is transferred, a fixing device 49 that fixes the toner image on the transfer material, and the like.
The photosensitive member 44 is a rotary drum type having a photosensitive layer on a conductive substrate, and is rotated at a predetermined peripheral speed (process speed) in the direction of the arrow. The charging roller 45 is set to a predetermined voltage by a power source applied from the AC power source 50, and is driven to rotate in accordance with the rotation of the photosensitive member brought into contact with the predetermined pressing force, thereby charging the photosensitive member to a predetermined potential. The latent image forming apparatus (not shown) includes an exposure apparatus such as a laser beam scanner that outputs a laser beam 41 that forms a latent image on the photosensitive member 44. By irradiating the photoconductor 44 with laser light 41 modulated by image information, an electrostatic latent image is formed on the uniformly charged photoconductor 44.
The electrostatic latent image formed on the photoconductor 44 is conveyed to a toner having the same polarity as that of the photoconductor 44 by a developing sleeve or a developing roller 46 disposed close to or in contact with the photoconductor 44, and is reversely developed. The electrostatic latent image is developed to form a toner image. The toner image on the photoconductor 44 is transferred to a transfer material 47 such as plain paper conveyed by a paper feed system between the transfer roller 42 and the photoconductor in the transfer device. Thereafter, in the fixing device 49, the toner image on the transfer material 47 is fixed on the transfer material by a heating roller or the like, and is discharged out of the apparatus to obtain an output image.
On the other hand, the residual toner on the photoconductor 44 is mechanically scraped off by the blade-type cleaning member 43 in the cleaning device 48 and is collected in the collection container of the cleaning device 48. 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.

[Process cartridge]
In the process cartridge according to the present invention, for example, the charging roller 45 made of the conductive member according to the present invention and another electrophotographic member, for example, the photosensitive member 44 are integrated, and can be attached to and detached from the main body of the electrophotographic apparatus. It is configured.
A sectional view of the process cartridge according to the present invention is shown in FIG. The process cartridge shown in FIG. 5 includes a photosensitive device 44, a charging device having a charging roller 45, a developing device having a developing roller 46, a toner supply roller 51 and a developing blade 52, a cleaning device 54 having a cleaning blade 53, and the like. It is integrated and detachable from the main body of the electrophotographic apparatus.

Examples of the present invention will be described below.
A: Coating liquid No. for conductive layer formation Preparation of 1-42;

<Preparation Example A1: Coating liquid No. Preparation of 1>
(1-1) Preparation of ionic conductive agent;
As an ionic conductive agent having a reactive functional group, 8.56 g (56.5 mmol) of glycidyltrimethylammonium chloride was dissolved in 50 ml of purified water and stirred for 1 hour to obtain an aqueous solution of the ionic conductive agent.
Next, 16.22 g (56.5 mmol) of cyclohexafluoropropane-1,3-bis (sulfonyl) imidolithium was dissolved in 50 ml of purified water and stirred for 1 hour.
The obtained aqueous solution was mixed and reacted by stirring for 2 hours. The reaction solution was allowed to stand for 12 hours, from an aqueous layer in which lithium chloride as a reaction byproduct was dissolved, and a glycidyltrimethylammonium salt ion conductive agent having cyclohexafluoropropane-1,3-bis (sulfonyl) imide. The oil layer was separated into two layers. The lower oil layer was recovered using a separatory funnel. Thereafter, the recovered oil layer was washed twice with purified water to remove a small amount of lithium chloride remaining in the oil layer, and an ionic conductive agent having a glycidyl group as a reactive functional group was produced.
(1-2) Synthesis of ion conductive resin;
Polypropylene glycol diglycidyl ether (weight average molecular weight: 640) and polypropylene glycol bis (2 aminopropyl ether) (weight average molecular weight: 400) were prepared as raw material polymers for the ion conductive resin.
0.47 g of the ionic conductive agent obtained in the above (1-1), 13.68 g (21.4 mmol) of polypropylene glycol diglycidyl ether, and 10.27 g (25.6 mmol) of polypropylene glycol bis (2 aminopropyl ether) It was dissolved in isopropyl alcohol (IPA) and adjusted so that the solid content was 27% by weight. 1 was prepared.

<Preparation Examples 2-42: Coating liquid No. Preparation of 2-42>
Except that the ion conductive agent species, the carrier molecular species subjected to ion exchange, the raw material of the ion conductive resin, and the addition amount of the ion conductive agent were changed as shown in Table 1, coating liquid No. As in the case of coating solution No. 2-42 were prepared.
In Table 1, symbols A-1 to A-7 representing ion conductive agent species, symbols B-1 to B-15 representing carrier molecular species subjected to ion exchange, and raw material monomers for ion conductive resin / The compound names indicated by symbols C-1 to C-11 representing raw material polymers are shown in Tables 2 to 4.

B: Elastic roller No. Creation of 1-2;
<Preparation Example B1: Elastic roller No. 1 creation)
Raw materials listed in Table 5 below were mixed with an open roll to obtain an unvulcanized rubber composition.

  Next, a device having a core bar supply mechanism and a conductive roller discharge mechanism is prepared in the cross head extruder, and a core bar conveying speed is 60 mm / sec, and a die having an inner diameter of φ12.5 mm is attached to the cross head. The extruder and crosshead were adjusted to 80 ° C. A layer of an unvulcanized rubber composition was formed around the core bar of a stainless steel rod having an outer diameter of 6 mm and a length of 258 mm supplied to the crosshead. Next, a core metal whose peripheral surface is coated with a layer of an unvulcanized rubber composition is placed in a hot air vulcanization furnace at 170 ° C. and heated for 60 minutes to crosslink the layer of the unvulcanized rubber composition. A rubber elastic layer was obtained. Thereafter, the end portion was cut and removed so that the length of the rubber was 228 mm. Finally, the surface of the rubber elastic layer was polished with a recovery grindstone and formed into a crown shape having a center diameter of 12 mm and an average diameter of 11.8 mm from the center to the left and right ends of 90 mm. 1 was obtained.

<Preparation Example B2: Elastic roller No. Creation of 2>
Except for using an unvulcanized rubber composition obtained by mixing the raw materials shown in Table 6 below with an open roll, the elastic roller No. 1 was used. In the same manner as in No. 1, the elastic roller no. 2 was created.

<Preparation Example B3: Elastic roller No. Create 3>
A stainless steel rod having a diameter of 6 mm and a length of 258 mm was placed in a cylindrical mold. The cavity of this cylindrical mold was filled with a liquid silicone rubber mixture made of the materials shown in Table 7 below.

  Next, the cylindrical mold was heated at a temperature of 120 ° C. for 8 minutes, then cooled to a temperature of 25 ° C., and the stainless steel rod having a silicone rubber layer formed on the peripheral surface was removed. Thereafter, the silicone rubber layer was treated at a temperature of 200 ° C. for 60 minutes to cure the silicone rubber layer, and an elastic roller No. 1 having an elastic body layer having a thickness of 3.0 mm formed on the peripheral surface of the stainless steel rod. 3 was obtained.

<Example 1: Charging roller No. Create 1>
Elastic roller No. 1 was applied to the previously prepared coating solution No. 1 dipping once, the coating liquid No. 1 coating film was formed. The dipping coating dipping time is 9 seconds, and the dipping coating lifting speed is adjusted so that the initial speed is 20 mm / sec and the final speed is 2 mm / sec. Between 20 mm / sec and 2 mm / sec, The speed was changed linearly.
Thereafter, the elastic roller 1 having a coating film formed on the surface was placed in an environment at a temperature of 25 ° C. for 30 minutes. Next, the elastic roller 1 is placed in a hot air circulating dryer set at a temperature of 90 ° C. for 1 hour, and further placed in a hot air circulating dryer set at a temperature of 160 ° C. for 1 hour to react the coating film on the elastic layer. A surface layer as a conductive layer was formed.
Thus, the charging roller No. 1 was obtained.
The obtained charging roller 1 was subjected to the following evaluation.

<Evaluation 1: Measurement of volume resistivity>
The current value of the charging roller was measured, and the volume resistivity of the charging roller 1 was calculated using the measurement result.
FIG. 2 is an explanatory diagram of a method for measuring the current value of the charging roller. As shown in FIG. 2, the charging roller is applied to the metal cylinder 22 having the same curvature as that of the photosensitive member in the electrophotographic apparatus with the same load as in the use state when used in the electrophotographic image forming apparatus. The current value is measured when a current is passed with the electrophotographic apparatus in contact with the same load as in the use state.
In FIG. 2A, 23a and 23b are bearings fixed to weights, and 21 is a charging roller as a subject. Then, stress that pushes vertically downward is applied to both ends of the conductive support 11 of the charging roller 21. A metal cylinder 22 is arranged vertically below the charging roller so that the charging roller 21 and the rotation axis are parallel to each other. Then, the charging roller is pressed against the bearings 23a and 23b as shown in FIG. 2B while rotating the metal cylinder 22 by a driving device (not shown). The metal cylinder 22 is rotated at the same speed as that of the photosensitive member in the state where the electrophotographic apparatus is used, and the DC voltage -200 V is applied by the power supply 24 while the charging roller 21 is rotated following the rotation of the metal cylinder 22. Two seconds after the voltage was applied, the time average of the current flowing out from the cylindrical metal 22 was measured with an ammeter A, and the time average of the results of measurement for 5 seconds was calculated.
In this evaluation, the charging roller No. as the subject is measured. Two 1s were prepared.
One charging roller No. 1 for a temperature of 23 ° C./humidity of 55% R.I. H. (N / N environment) for 48 hours, charging roller No. 1 was acclimatized. Thereafter, in the same environment, the charging roller No. Applying a force of 5N to both ends of the shaft 1 to bring it into contact with a cylindrical metal having a diameter of 30 mm, rotating the cylindrical metal at a peripheral speed of 150 mm / s, measuring the current value, and obtaining the electric resistance value It was.
The other charging roller No. 1 for a temperature of 15 ° C./humidity of 10% R.P. H. (L / L environment) was allowed to acclimate to the L / L environment for 48 hours. Thereafter, in the same environment, the charging roller No. Applying a force of 5 N to both ends of the shaft 1 to bring it into contact with a cylindrical metal with a diameter of 30 mm, rotating the cylindrical metal at a peripheral speed of 150 mm / s, measuring the electrical resistance value, and calculating the electrical resistivity Asked.
In addition, the charging roller No. in the L / L environment. No. 1 charging roller No. 1 in an N / N environment. Divided by the electrical resistivity of 1 and logarithmically converted was taken as the environmental fluctuation digit. As a result, the charging roller No. The environmental variation dependency of the electrical resistivity of 1 can be evaluated.

<Evaluation 2: Bleed evaluation>
Charging roller No. 1 is placed on a polyethylene terephthalate (PET) sheet, and the charging roller No. 1 is set. A load of 500 g is applied to both ends of the shaft of No. 1 to charge the charging roller no. The surface of 1 was brought into contact with a PET sheet. This state was measured at a temperature of 40 ° C./humidity of 95% R.D. H. For one week. After that, the charging roller No. 1 is removed from the PET sheet, and the charging roller No. 1 of the PET sheet is removed. The surface on which 1 was in contact was observed with an optical microscope (10 times). Charging roller No. Whether or not the bleed from the elastic layer 1 adhered to the surface of the PET sheet through the surface layer was evaluated based on the criteria described in Table 8 below.

<Evaluation 3: Evaluation of charging ability>
An electrophotographic laser printer (trade name: Laserjet 4700dn) was modified so that the output speed of the recording medium was 300 mm / sec. As the charging roller of this modified laser printer, charging roller No. 1 was installed. Note that the image resolution of this laser printer is 600 dpi.
By causing the laser printer to perform an intermittent image forming operation, 40001 electrophotographic images were output. In the intermittent image forming operation, after outputting two images, the rotation of the electrophotographic photosensitive drum is stopped for about 3 seconds, and the image forming operation is performed again. Further, as the images output at this time, the first to 40000th sheets were character images having a printing density of 1%, and the last sheet was a halftone image. Here, the halftone image is an image in which a horizontal line having a width of 1 dot and an interval of 2 dots is drawn in the direction perpendicular to the rotation direction of the electrophotographic photosensitive member. Then, the 40th halftone image was visually observed and evaluated according to the criteria shown in Table 9 below.

<Evaluation 4: Evaluation by Spotted Image Defect>
As a charging roller for an electrophotographic laser printer (trade name: Laserjet 4515n, manufactured by HP), a charging roller No. 1 is used. 1 was installed. The output speed of the recording medium of this laser printer is 370 mm / sec, and the image resolution is 1200 dpi.
By causing the laser printer to perform an intermittent image forming operation, 40,000 electrophotographic images were output. In the intermittent image forming operation, after outputting two images, the rotation of the electrophotographic photosensitive drum is stopped for about 3 seconds, and the image forming operation is performed again.
The image output at this time is an H-Line image. The H-Line image was an image in which a horizontal line having a width of 2 dots and an interval of 176 dots was drawn in the direction perpendicular to the rotation direction of the electrophotographic photosensitive member.
Thereafter, a halftone image was output while raising the DC applied voltage −600 V, the frequency 2931 Hz, and the AC applied voltage from Vpp = 1200 V, and the voltage at which the spot-like image defects disappeared was measured. In this evaluation, it can be said that the lower the voltage at which the spot-like image defect disappears, the charging roller has a uniform electric resistance value.

<Evaluation 5: Molar ratio of carrier molecules according to the present invention to all carrier molecules in the conductive layer>
The surface layer of the charging roller 1 was scraped and dissolved in a dilute aqueous solution of hydrochloric acid to extract carrier molecules in the ion conductive resin. The aqueous solution after extraction is dried, the extract is collected, mass spectrometry using a time-of-flight mass spectrometer (TOF-MS) and ICP emission analysis are performed, and the amount of all carrier molecules present in the surface layer, and The amount of the carrier molecule according to the present invention was detected, and the molar ratio of the carrier molecule according to the present invention to the total carrier molecules in the conductive layer was determined.

<Examples 2 to 42>
In the formation of the conductive layer as the surface layer, No. 1 shown in Table 10 was used. The charging roller No. 1 was the same as the charging roller 1 except that the coating solution was used. 2-42 were made. These charging rollers were evaluated in the same manner as the charging roller 1.

<Examples 43 to 53>
Elastic roller No. 1 is an elastic roller no. 2 and the formation of the surface layer was changed to No. 1 described in Table 11. The charging roller No. was used except that the coating liquid was used. In the same manner as in No. 1, the charging roller no. 43 to 53 were prepared and used for Evaluation 1 to Evaluation 5. The results are also shown in Table 11.

<Example 54>
A stainless steel rod having a diameter of 6 mm and a length of 258 mm was placed in a cylindrical mold. In the cavity of this cylindrical mold, the coating liquid No. The resin mixture excluding IPA from 3 was injected and filled. Next, the cylindrical mold was heated at a temperature of 90 ° C. for 1 hour, and further heated at a temperature of 160 ° C. for 1 hour. Thereafter, the cylindrical mold was cooled to a temperature of 25 ° C., and the stainless steel rod having a conductive layer having a thickness of 3.0 mm formed on the peripheral surface was removed. This is the charging roller No. 54. This charging roller No. 54 was subjected to Evaluation 1 to Evaluation 5. The results are shown in Table 12.

<Example 55>
Elastic roller No. A protective layer was provided on 10 surface layers according to the following method.
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution to adjust the solid content to 10% by mass. 15 parts by mass of carbon black (HAF), 35 parts by mass of acicular rutile-type titanium oxide fine particles, 0.1 part by mass of modified dimethyl silicone oil, hexamethylene diisocyanate (HDI) with respect to 100 parts by mass of the solid content of the acrylic polyol solution described above ) And isophorone diisocyanate (IPDI) 7: 3 mixture of each butanone oxime block, 80.14 parts by mass were prepared to prepare a mixed solution. At this time, the mixture of the block HDI and the block IPDI was added so that “NCO / OH = 1.0”.

  In a 450 mL glass bottle, 210 g of the above mixed solution and 200 g of glass beads having an average particle diameter of 0.8 mm were mixed as media, and dispersed for 24 hours using a paint shaker disperser. After dispersion, 5.44 parts by mass of crosslinked acrylic particles (trade name: MR50G; manufactured by Soken Chemical Co., Ltd.) as resin particles were added (equivalent to 20 parts by weight with respect to 100 parts by weight of acrylic polyol), and then dispersed for 30 minutes. Thus, a paint for forming a protective layer was obtained.

  The obtained coating material for forming a protective layer was dipped once on the outer periphery of the charging roller of Example 10 and air-dried at room temperature for 30 minutes or more. Subsequently, it dried for 1 hour with the hot air circulating dryer set to 90 degreeC, and also dried for 1 hour with the hot air circulating dryer set to 160 degreeC, and formed the outermost layer on the charging roller. The dipping coating dipping time is 9 seconds, and the dipping coating lifting speed is adjusted so that the initial speed is 20 mm / sec and the final speed is 2 mm / sec. Between 20 mm / sec and 2 mm / sec, the speed is linear. The speed was changed. As described above, the charging roller No. 1 having the protective layer is provided. 55 was created. This charging roller No. 55 was subjected to Evaluation 1 to Evaluation 5. The results are shown in Table 12.

<Comparative Example 1>
In Preparation Example 1 (1-2), except that glycidyltrimethylammonium chloride was used as the ionic conductive agent, the coating solution No. 1 was prepared in the same manner as in Preparation Example 1 (1-2). 43 was prepared.
For forming the surface layer, coating liquid No. Except for using No. 43, the charging roller no. C-1 was prepared and used for evaluations 1-5. The results are shown in Table 13.
For evaluation 5, the charging roller no. The carrier molecules contained in the conductive layer of C-1 were only chloride ions. Chlorine ions do not fall under the carrier molecule according to the present invention. Therefore, the result of evaluation 5 was 0 mol%.

<Comparative example 2>
In Preparation Example 1 (1-2), except that trimethylhexylammonium-bis (trifluoromethanesulfonyl) imide was used as the ionic conductive agent, the coating solution No. was the same as (1-2) in Preparation Example 1. . 44 was prepared.
For forming the surface layer, coating liquid No. Except for using No. 44, the charging roller no. C-2 was prepared and used for evaluations 1-5. The results are shown in Table 13.
The ionic conductive agent according to this comparative example does not have a reactive functional group. Therefore, the binder resin according to this comparative example does not have a quaternary ammonium group and a sulfonic acid group in the molecular structure, and does not correspond to the ion conductive resin according to the present invention.

<Comparative Example 3>
In Preparation Example 1 (1-2), coating solution No. 1 was prepared in the same manner as Preparation Example 1 (1-2) except that stearic acid-bis (trifluoromethanesulfonyl) imide was used as the ionic conductive agent. 45 was prepared.
For forming the surface layer, coating liquid No. Except for using 45, the charging roller no. C-3 was prepared and used for evaluations 1-5. The results are shown in Table 13.
In addition, the ionic conductive agent used in this comparative example has a carboxyl group and an ion exchange group. Therefore, the binder resin according to this comparative example does not have a quaternary ammonium group and a sulfonic acid group in the molecular structure, and does not correspond to the ion conductive resin according to the present invention.

<Example 56>
Elastic roller No. 3 and coating liquid No. 3 for forming the surface layer. 4 except that the developing roller No. 4 was used in the same manner as in Example 1. 1 was created.
Development roller No. 1 was subjected to Evaluation 1, Evaluation 2, Evaluation 5, and Evaluation 6 below.

<Evaluation 6: Electrophotographic image formation test>
As an electrophotographic apparatus, a laser printer (trade name: LBP5400, manufactured by Canon Inc.) was prepared. Then, the contact pressure between the developing roller and the photosensitive member and the penetration amount were adjusted so that the toner coating amount on the developing roller was 0.35 mg / cm ² . Also, a toner supply roller made of a soft urethane sponge is provided to scrape old toner from the developing roller and supply new toner to the developing roller.
As a developing roller of this laser printer, a developing roller No. No. 1 was mounted, and 20000 electrophotographic images were continuously formed so as to draw a horizontal line having a width of 2 dots and an interval of 50 dots in the direction perpendicular to the rotation direction of the photosensitive member. Subsequently, one halftone image was formed. This halftone image was visually observed and evaluated according to the criteria described in Table 14 below. The results are shown in Table 15.

<Examples 57 to 59>
No. shown in Table 15 for the formation of the surface layer. A developing roller No. was prepared in the same manner as in Example 56 except that the above coating solution was used. 2-4 were created and used for Evaluation 1-2, Evaluation 5 and Evaluation 6. The results are also shown in Table 15.

(Comparative Example 4)
Coating liquid No. 4 is the coating liquid No. A developing roller C-4 was prepared in the same manner as in Example 56 except that the surface layer was changed to 44 and subjected to evaluations 1, 2, 5 and 6. The results are shown in Table 16.
In addition, the ionic conductive agent which concerns on this comparative example does not have a reactive functional group. Therefore, the binder resin according to this comparative example does not have a quaternary ammonium group and a sulfonic acid group in the molecular structure, and does not correspond to the ion conductive resin according to the present invention.

11 Core 12 Elastic layer 13 Surface layer 14 Intermediate layer

Claims (8)

A conductive member for electrophotography having a conductive support and a conductive layer,
The conductive layer is
An ion conductive resin having a quaternary ammonium ion in the molecular structure as a binder resin, and
A conductive member comprising carrier molecules represented by the following formula (5):

(Wherein (in 5), _{R 1} is. Representing the ethyl group, n- butyl group, sec- butyl group, tert- butyl group, n- hexyl, n- octyl or n- decyl). A conductive member for electrophotography having a conductive support and a conductive layer,
The conductive layer is
Containing an ion conductive resin having a sulfonate ion in the molecular structure as a binder resin; and
A conductive member comprising carrier molecules represented by the following formula (6) or (7):

(In Formula (6) and Formula (7), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. And may contain a heteroatom). A conductive member for electrophotography having a conductive support and a conductive layer,
The conductive layer is
Containing an ion conductive resin having a sulfonate ion in the molecular structure as a binder resin; and
A conductive member comprising carrier molecules represented by the following formula (8) or (9):

(In Formula (8) and Formula (9), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and includes a hetero atom. May be.) A conductive member for electrophotography having a conductive support and a conductive layer,
The conductive layer is
Containing an ion conductive resin having a sulfonate ion in the molecular structure as a binder resin; and
A conductive member comprising carrier molecules represented by the following formula (10):

(In Formula (10), R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and may include a hetero atom). The electroconductive member as described in any one of Claims 1-4 which has an ethylene oxide unit in the molecular structure of the said ion conductive resin. The conductive member according to claim 5, wherein the ion conductive resin is a phenol resin. An electrophotographic apparatus comprising the conductive member according to claim 1. A process cartridge comprising the conductive member according to any one of claims 1 to 6 and configured to be detachable from a main body of an electrophotographic apparatus.

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