JP2866452B2 - Charging member - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a charging member, and more particularly to a charging member used for primary charging, transfer charging, and charge removal in electrophotography.

[Prior art] The charging process in an electrophotographic process using an electrophotographic photoreceptor has been performed by applying a high voltage (DC) to a metal wire.
(5-8 kV) is applied and charging is performed by the corona generated. However, in this method, ozone or NO _X
There is a problem that the surface of the photoreceptor is deteriorated by corona products such as the above, causing image blurring and deterioration, and contamination of the wire affects the image quality, resulting in image white spots and black stripes.
On the other hand, the electric current flowing toward the photoreceptor was only 5 to 30% of the electric current, and most of the electric current flowed to the shield plate and was ineffective as a charging means.

In order to compensate for such disadvantages, direct charging methods have been studied and many proposals have been made (JP-A-57-178267, JP-A-56-104351, JP-A-58-40566, JP-A-58-40566). -139156, JP-A-58-150975, etc.). However, even if the photoconductor is charged by the contact charging method as described above, each portion of the photoconductor surface is not uniformly charged,
Spot-like uneven charging occurs. For example, in the reversal development method, even if a process of light image exposure or less is applied to the photosensitive member in the spot-like uneven charging state, the output image becomes a spot-like black spot image corresponding to the spot-like charging unevenness, and the regular developing method uses the spot-like black spot image. The image becomes a spot-like white spot image with respect to unevenness, and a high-quality image cannot be obtained.

Further, the direct charging method has no market record in spite of many proposals. The reasons for this include the uniformity of charging and the occurrence of discharge breakdown of the photoconductor due to the direct application of voltage. One breakdown point due to discharge breakdown, for example, in the case of a cylindrical photosensitive member, has a drawback that charging in the entire axial direction flows to the breakdown point and the charge is no longer charged.

[Problem to be Solved by the Invention] A method of forming a resin layer on the surface to prevent the dielectric breakdown has also been reported. However, these materials also have large fluctuations in resistance under low temperature and low humidity, and their chargeability is unstable. The resin on the surface of the photoconductor and the resin on the surface of the charging member were compatible with each other and had defects such as sticking.

Accordingly, an object of the present invention is to solve the above-mentioned drawbacks and to provide a spot-like fog due to non-uniform charging, and to stably supply a high-quality image free from image defects and the like due to discharge breakdown of a photoconductor. It is to provide a member.

[Means for Solving the Problems] That is, the present invention provides a charging member having a conductive elastic layer on a conductive support, wherein the conductive elastic layer has a resin layer containing a polyetheramideimide resin on the conductive elastic layer. A charging member characterized in that:

 Hereinafter, the present invention will be described in more detail.

As shown in FIG. 1, the charging member of the present invention is provided with a conductive elastic layer 2 on a conductive support 1a, and a resin layer 3 containing a polyetheramideimide resin on the elastic layer 2.
Is a three-layer configuration provided with a.

The polyether amide imide resin used as the resin layer of the present invention may be formed by trimellitic acid or a reactive acid derivative thereof, for example, trimellitic anhydride, trimellitic anhydride chloride and a compound represented by the general formula (I): (Wherein, R _{1 to} R ₄ are hydrogen atoms; alkyl groups such as methyl, ethyl, propyl, iso-propyl, butyl and sec-butyl; alkoxy groups such as methoxy and ethoxy; or chlorine,
Represents a halogen atom such as bromine; R ₅ and R ₆ represent a hydrogen atom; a substituted or unsubstituted alkyl group such as methyl, ethyl, trifluoromethyl and trichloromethyl; and an alkenyl group such as a vinyl group). With an aromatic diamine having the following formula (for example, JP-B-44-19274, JP-B-49-4077, JP-B-42-15637,
JP-A-57-14622), precipitation polymerization method (for example, JP-B-54-44719), non-aqueous dispersion polymerization method (for example,
U.S. Pat. No. 4,427,822), a melt polymerization method (Japanese Patent Publication No. Sho 4)
No. 0-8910) and the like. In view of cost, a solution polymerization method in which trimellitic anhydride and a diamine are polycondensed in the presence of a dehydration catalyst such as phosphoric acid is preferable.

It is preferable to use 90 to 130 mol% of the total amount of trimellitic acid or this reactive acid derivative with respect to the aromatic diamine having an ether bond represented by the general formula (I),
Particularly, it is preferable to use 100 mol% or almost 100 mol%.

As the aromatic diamine having an ether bond represented by the general formula (I) in the present invention, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-bromo-4
-(4-aminophenoxy) phenyl] propane, 2,2
-Bis [3-ethyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-propyl-4-
(4-aminophenoxy) phenyl] propane, 2,2-
Bis [3-isopropyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-butyl-4
-(4-aminophenoxy) phenyl] propane, 2,2
-Bis [3-sec-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methoxy-
4- (4-aminophenoxy) phenyl] propane, 2,
2-bis [3-ethoxy-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-
4- (4-aminophenoxy) phenyl] propane, 2,
2-bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (4-aminophenoxy) phenyl] propane, 2,
2-bis [3,5-dimethoxy-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4
-(4-aminophenoxy) -5-methylphenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3
-Chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-bromo-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-ethyl-
4- (4-aminophenoxy) phenyl] ethane, 1,1
-Bis [3-propyl-4- (4-aminophenoxy)
Phenyl] ethane, 1,1-bis [3-isopropyl-4
-(4-aminophenoxy) phenyl] ethane, 1,1-
Bis [3-butyl-4- (aminophenoxy) phenyl] ethane, 1,1-bis (3-sec-butyl-4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3
-Methoxy-4- (4-aminophenoxy) phenyl]
Ethane, 1,1-bis [3-ethoxy-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, 1-bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] ethane,
1-bis [3,5-dimethoxy-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4-
(Aminophenoxy) -5-methylphenyl] ethane,
Bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy)
Phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3-bromo-
4- (4-aminophenoxy) phenyl] methane, bis [3-ethyl-4- (4-aminophenoxy) phenyl] methane, bis [3-propyl-4- (4-aminophenoxy) phenyl] methane, bis [ 3-isopropyl-4- (4-aminophenoxy) phenyl] methane, bis [3-butyl-4- (4-aminophenoxy) phenyl] methane, bis [3-sec-butyl-4- (4-aminophenoxy) Phenyl] methane, bis [3-methoxy-4- (4-aminophenoxy) phenyl] methane, bis [3-ethoxy-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] methane,
Bis [3,5-dibromo-4- (4-aminophenoxy)
Phenyl] methane, bis [3,5-dimethoxy-4- (4
-Aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) -5-methylphenyl] methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis [4- (4
-Aminophenoxy) phenyl] propane, 3,3-bis [4- (4-aminophenoxy) phenyl] pentane,
1,1-bis [4- (4-aminophenoxy) phenyl]
Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3 , 3-Hexachloro-2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 3,3-bis [3,5-dimethyl-4-
(4-aminophenoxy) phenyl] pentane, 1,1-
Bis [3,5-dimethyl-4- (4-aminophenoxy)
Phenyl] propane, 1,1,1,3,3,3-hexafluoro-
2,2-bis [3,5-dibromo-4 (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro-2,2-bis [3,5-dibromo-4 -(4-aminophenoxy) phenyl] propane, 3,3-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] pentane,
1,1-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3- Methyl-4- (4-aminophenoxy) phenyl] butene, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo- 4- (4-aminophenoxy) phenyl] butane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-
4- (4-aminophenoxy) phenyl] propane and the like. Among these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is representative. If necessary, mixtures of the above diamines can be used.

Further, in the present invention, if necessary, a known diamine such as 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4 ′
-Benzophenone diamine, metaphenylenediamine,
4,4'-di (4-aminophenoxy) phenylsulfone, paraphenylenediamine, 4,4'-di (3-aminophenoxy) phenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, 1,3 -Bis (4-aminophenoxy) benzene, and for example (Where m is a number in the range of 1 to 100). The ratio of these diamines to the whole diamines is desirably 30 mol% or less. If this ratio exceeds 30 mol%, the solubility of the resin is adversely affected, which is not preferable. The polyetheramideimide polymer thus obtained is represented by the general formula (II) And a repeating unit represented by the general formula (III) Is considered to be a polymer in which the repeating units represented by are appropriately bonded to each other and to each other. However, in the general formulas (II) and (III), A represents a benzene ring;
Represents a residue obtained by removing the amino group of any of the above diamines. When a repeating unit of the general formula (II) and a repeating unit of the general formula (III) are bonded, one B is bonded to the other N doing.

These specific polyether amide imide resins are different from conventional polyamide imide resins in tetrahydrofuran,
Since it is soluble in relatively low-boiling general-purpose organic solvents such as dioxane, 1,2-dimethoxyethane, cyclohexanone, and 4-methylcyclohexanone, it is easy to adjust the coating solution and the coating film can be dried at a low temperature in a short time. There is. Also, the obtained resin layer is hard and tough.

Further, a binder resin may be added to the resin layer.
However, the amount of binder resin added is 30% by weight based on the total resin.
The following is preferred. As a binder resin in the resin layer, polymethyl methacrylate, acrylic resin such as polybutyl methacrylate, polyvinyl butyral, polyvinyl acetal, polyarylate, polycarbonate,
Phenoxy resin, polyvinyl acetate, polyvinyl pyridine and the like can be mentioned.

Since the conventional charging member has a surface made of rubber or polyurethane, if the electrophotographic photoreceptor is kept in contact, the photoreceptor and the charging member are fixed, or a hard surface is wrinkled, Image defects occurred.

On the other hand, the charging member having the resin layer containing the polyetheramideimide resin of the present invention has low adhesion to the electrophotographic photoreceptor and has high flexibility, so that a high-quality image is provided, and Thus, the resin layer has a small change in volume resistance even under low temperature and low humidity, and can be used as a stable charging member.

The thickness of the resin layer is preferably in the range of 5 to 500 μm, particularly preferably 20 to 200 μm.

The volume resistivity of the resin layer is preferably in the range of 10 ⁶ to 10 ¹² Ω · cm. Further, as disclosed in Japanese Patent Application No. 62-230334, the volume resistivity of the resin layer is preferably larger than the volume resistivity of the lower conductive elastic layer in contact with the resin layer. 10 ⁰ to 10 ¹¹ Omega is a volume resistivity of the elastic layer · cm, preferably in the range of particularly ^{10 2} ~10 10 Ω · cm. Aluminum, iron,
Metals such as copper, conductive polymers such as polyacetylene, polypyrrole, and polythiophene, rubber and plastic elastomers in which carbon and metal, etc. are dispersed and subjected to conductive treatment, the surface of rubber or plastic elastomer is metal or other conductive material. Laminated ones can be used. Further, the elastic layer 2 may have a multilayer structure in which functions are separated as necessary. Iron, copper, stainless steel, or the like can be used as the conductive support 1a.

Further, as shown in FIG. 2, a protective layer 4 may be provided on the surface of the charging member to protect the charging member. This protective layer is formed of a resin layer, and may be mixed with conductive particles therein to control conductivity and insoluble resin powder 5 to control surface roughness of the charging member.

In the case of a blade-shaped charging member as shown in FIG. 3, a conductive elastic layer 2 is provided on a conductive sheet metal 1b, and a resin layer 3
Is provided.

 Further, a protective layer may be provided.

The shape of the charging member may be any of a roller shape and a blade shape, but is preferably a roller shape in terms of uniform charging.

The electrophotographic photoreceptor is based on a configuration in which a photosensitive layer is provided on a conductive support. As the conductive support, a support having conductivity itself, for example, aluminum, an aluminum alloy, stainless steel, chromium, titanium, or the like can be used.In addition, aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can be used. A conductive support having a layer formed by vacuum deposition, plastic, a support in which conductive particles (eg, carbon black, tin oxide particles, etc.) are impregnated with a suitable binder into plastic or paper, and a conductive binder. Plastic or the like can be used.

An undercoat layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. The undercoat layer can be formed of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane, gelatin, aluminum oxide, or the like. The thickness of the undercoat layer is 5 μm or less, preferably 0.5 to 3 μm.
m is appropriate. The undercoat layer preferably has a resistivity of 10 ⁷ Ω · cm or more in order to exhibit its function.

The photosensitive layer is formed, for example, by coating a photoconductor such as an organic photoconductor, amorphous silicon, or selenium with a binder as necessary, and then forming the coating or vacuum deposition. When an organic photoconductor is used, a photosensitive layer composed of a combination of a charge generation layer that generates charge carriers upon exposure and a charge transport layer capable of transporting the generated charge carriers can also be used effectively.

The charge generation layer is formed by depositing one or more kinds of charge generation materials such as azo pigments, quinone pigments, quinone anine pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, and quinacdrine pigments, or It can be formed by dispersing together with a binder (even without a binder) and coating.

The binder can be selected from a wide range of insulating resins or organic photoconductive polymers. For example, as the insulating resin, polyvinyl butyral, polyarylate (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, acrylic resin, polyacrylamide resin, polyamide, cellulose resin, urethane resin, epoxy resin, Casein, polyvinyl alcohol and the like can be mentioned. Examples of the organic photoconductive polymer include carbazole, polyvinyl anthracene, and polyvinyl pyrene.

The thickness of the charge generation layer is 0.01 to 15 μm, preferably 0.05 to
5 μm, and the weight ratio between the charge generation layer and the binder is 10: 1 to
1:20.

The solvent used for the coating for the charge generation layer is selected from the solubility and dispersion stability of the resin and the charge transporting material used. As the organic solvent, alcohols, sulfoxides, ethers, esters, and aliphatic halides are used. Hydrocarbons or aromatic compounds can be used.

Coating can be performed using a coating method such as a dip coating method, a spray coating method, a Meyer bar coating method, and a blade coating method.

The charge transport layer is formed by dissolving a charge transport material in a film-forming resin. Examples of the organic charge transporting material used in the present invention include hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, thiazole compounds, and triarylmethane compounds. These charge transport materials can be used alone or in combination of two or more.

Examples of the binder used for the charge transport layer include phenoxy resin, polyacrylamide, polyvinyl butyral, polyarylate, polysulfone, polyamide, acrylic resin, acrylonitrile resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenolic resin, epoxy Resin, polyester, alkyd resin, polycarbonate,
Polyurethane or a copolymer containing two or more of the repeating units of these resins, such as a styrene-butadiene copolymer, a styrene-acrylonitrile polymer, and a styrene-maleic acid copolymer can be used. In addition, organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene can be selected.

The thickness of the charge transport layer is 5 to 50 μm, preferably 8 to 20 μm.
m, and the weight ratio of the charge transport material to the binder is 5: 1 to 1:
5, preferably about 3: 1 to 1: 3. The coating can be performed by the coating method as described above.

Furthermore, since dyes, pigments, organic charge transporting substances, and the like are generally vulnerable to contamination by ultraviolet rays, ozone, oil, and the like, metals, and the like, a protective layer may be provided as necessary. To form an electrostatic latent image on this protective layer, the surface resistivity must be 10 ¹¹ Ω
It is desirable that this is the case.

The protective layer of the photoconductor is made of a resin such as polyvinyl butyral, polyester, polycarbonate, acrylic resin, methacrylic resin, nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer. A solution dissolved by a solvent can be formed on the photosensitive layer by coating and drying. At this time, the thickness of the protective layer is generally in the range of 0.05 to 20 μm. The protective layer may contain an ultraviolet absorber or the like.

The charging member of the present invention can be applied to, for example, an electrophotographic apparatus as shown in FIG. In this apparatus, a primary charging member 6, an image exposure unit 7, a developing unit 8, a corona charger 9 for transfer charging, a cleaning unit 10, and a pre-exposure unit 11 are arranged on a peripheral surface of an electrophotographic photosensitive member 12. .

A voltage (for example, a pulsating voltage in which a DC voltage of 200 V or more and 2000 V or less and an AC voltage of 4000 V or less between peaks are superimposed) is externally applied to the primary charging member 6 which is arranged in contact with the electrophotographic photosensitive member 12. Then, the surface of the electrophotographic photosensitive member 12 is charged, and the image on the original is image-exposed to the photosensitive member by the image exposure means 7 to form an electrostatic latent image. Next, the electrostatic latent image on the photoconductor is developed (visualized) by adhering the developer in the developing means 8 to the photoconductor, and the developer on the photoconductor is transferred to a corona charger for charging. The developer is transferred to a transfer member 13 such as paper by 9, and the developer remaining on the photoconductor without being transferred to the paper at the time of transfer by the cleaning unit 10 is collected.

An image can be formed by such an electrophotographic process, but if residual charges remain on the photoconductor, light is applied to the photoconductor by the pre-exposure unit 11 before primary charging to remove the residual charges. You had better.

When the charging member of the present invention is used for transfer charging, it can be applied to, for example, an electrophotographic apparatus as shown in FIG. In this apparatus, a primary charging corona charger 14, an image exposure means 7, a developing means 8, a transfer charging member 15, a cleaning means 10, and a pre-exposure means 11 are arranged on the peripheral surface of an electrophotographic photosensitive member 12. I have.

A voltage (for example, a DC voltage of 400 to 1000 V) is applied to the transfer charging member 15 which is arranged in contact with the electrophotographic photosensitive member 12 to transfer the developer on the electrophotographic photosensitive member to a transfer member such as paper. Can be.

When the charging member of the present invention is used for static elimination charging, it can be applied to, for example, an electrophotographic apparatus as shown in FIG. In this apparatus, a primary charging corona charger 14, an image exposure unit 7, a developing unit 8, a transfer charging corona charger 9, and a cleaning unit 10 are arranged on a peripheral surface of an electrophotographic photosensitive member 12.

A voltage (for example, an AC peak-to-peak voltage of 500 to 2000) is applied to the charging member 16 for discharging and charging, which is disposed in contact with the electrophotographic photosensitive member 12.
V) can be applied to eliminate charges on the electrophotographic photosensitive member.

The charging member of the present invention exerts its characteristics remarkably by being applied to an electrophotographic photosensitive member having a photosensitive layer containing an organic photoconductor, which is susceptible to deterioration in mechanical strength and chemical stability. can do.

The charging member to be brought into contact with the photoreceptor in the present invention is not limited to a specific method, and the charging member may be a fixed type or a moving type such as rotating in the same direction or the opposite direction to the photoreceptor. it can. Further, it is also possible for the charging member to function as a developer cleaning device on the photosensitive member.

Applied voltage to the charging member in the direct charging of the present invention,
Regarding the application method, it depends on the specifications of each electrophotographic apparatus, but in addition to the method of applying the desired voltage instantaneously, the method of gradually increasing the applied voltage for the purpose of protecting the photoreceptor, the method of applying DC to AC Can be applied in the order of DC AC or AC DC in the case of superimposing.

When the charging member of the present invention is used for primary charging of an electrophotographic apparatus, it is necessary to superimpose a DC voltage and an AC voltage on an electrophotographic photosensitive member in an image output area.

When primary charging is applied only with a DC voltage, uniform charging cannot be performed. When used for transfer charging, a DC voltage alone or a DC voltage and an AC voltage may be superimposed. When used for static elimination charging, it is necessary to apply only an AC voltage.

In the present invention, processes such as image exposure, development, and cleaning can employ any method known in the field of electrostatography, and are not limited to a specific type such as a type of developer. The charging member of the present invention is not limited to a copying machine, but may be a laser printer or a CRT printer,
It can also be used in electrophotographic application fields such as facsimile machines having an electrophotographic plate making system and a receiving means for receiving image information from a remote terminal.

[Examples] Next, the present invention will be described in detail based on the present examples, but the present invention is not limited thereto.

First, materials and synthesis methods of four types of polyetheramideimide resins used in the resin layer will be described.

◎ Synthetic components of polyetheramide imide resin (A) Parts by weight Trimellitic acid in water 10 2,2-bis [4- (4-aminophenoxy) phenyl] propane 20 N-methylpyrrolidone 30 Phosphoric acid aqueous solution (phosphoric acid) 0.3% The above ingredients are stirred into a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and moisture meter.
The temperature was raised to 160 ° C. while passing nitrogen gas. The temperature was gradually increased, and the temperature was raised to 205 ° C. while removing distilling water out of the system, and the reaction was carried out in a temperature range of 205 to 210 ° C. The reaction end point was controlled by Gardner viscosity to obtain a polyetheramide imide resin having a reduced viscosity (dimethylformamide, 0.5 g / dl, 30 ° C., the same applies hereinafter) of 0.41 (dl / g). The obtained polyetheramideimide resin solution was diluted with N-methylpyrrolidone to about 25% by weight, and this solution was dropped into strongly stirred water with a mixer to recover a solid polyetheramideimide resin. . After the solid resin was thoroughly washed with hot water, it was washed by boiling with a large amount of water. After filtering this,
It was dried with a hot air dryer at 150 ° C. for 6 hours to obtain a powdered polyetheramideimide resin (A).

◎ Synthesis of polyether amide imide resin (B) The same operation was carried out using the same components as resin A, using the same apparatus, except that the reaction end point was controlled by Gardner viscosity, and the reduced viscosity was 0.69 (dl / g). ) A powder polyetheramideimide resin (B) was obtained.

◎ Synthetic components of polyetheramide imide resin (C) Parts by weight trimellitic acid in water 10 2,2-bis [4- (4-aminophenoxy) phenyl] propane 20 N-methylpyrrolidone 30 Phosphoric acid aqueous solution (phosphoric acid) 0.3% The above ingredients are stirred into a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and moisture meter.
The temperature was raised to 160 ° C. while passing nitrogen gas. The temperature was gradually increased, and the temperature was raised to 205 ° C. while removing distilling water out of the system, and the reaction was carried out in a temperature range of 205 to 210 ° C. The end point of the reaction was controlled by Gardner viscosity to obtain a polyetheramideimide resin having a reduced viscosity (dimethylformamide, 0.5 g / dl, 30 ° C., the same applies hereinafter) of 0.43 (dl / g). The obtained polyetheramideimide resin solution was diluted with N-methylpyrrolidone to about 25% by weight, and this solution was dropped into strongly stirred water with a mixer to recover a solid polyetheramideimide resin. . After the solid resin was thoroughly washed with hot water, it was washed by boiling with a large amount of water. After filtering this,
The powder was dried with a hot air dryer at 150 ° C. for 6 hours to obtain a powdered polyetheramideimide resin (C).

◎ Synthesis of polyether amide imide resin (D) The same operation was carried out using the same components as resin A, using the same apparatus, except that the reaction end point was controlled by Gardner viscosity and reduced viscosity was 0.68 (dl / g). )) To obtain a powdered polyetheramideimide resin (D).

Example 1 An aluminum cylinder having a thickness of 0.5 mm and a diameter of 60 mm × 260 mm was prepared as a conductive support.

Copolymer nylon (trade name: CM8000, manufactured by Toray Industries, Inc.) 4
Part and type 8 nylon (trade name: Lacamide 500
3, Dainippon Ink Co., Ltd.) 4 parts methanol 50 parts, n
-Dissolved in 50 parts of butanol and dip-coated on the support to form a 0.6 μm thick undercoat layer.

10 parts of disazo pigment of the following structural formula, And polyvinyl butyral resin (trade name: Eslec BM
2, Sekisui Chemical Co., Ltd.) and 10 parts of cyclohexanone were dispersed in a sand mill for 10 hours. 30 parts of methyl ethyl ketone was added to the dispersion, and the dispersion was applied on the undercoat layer.
A charge generating layer having a thickness of 15 μm was formed.

Prepare 10 parts of polycarbonate Z resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a weight average molecular weight of 120,000, and prepare a hydrazone compound having the following structural formula. It was dissolved in 80 parts of monochlorobenzene together with 10 parts. This was applied on the charge generation layer to form a charge transport layer having a thickness of 16 μm, thereby producing an electrophotographic photosensitive member No. 1.

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
Melt and knead parts by weight, φ8 ×
It was formed into a diameter of 20 × 240 mm through a stainless steel shaft of 260 mm, and a conductive elastic layer of a roller-shaped charging member was provided.

The volume resistance of the conductive elastic layer of the charging member is set to 22
It is 3 × 10 ⁴ Ω · cm when measured in an environment of 60 ° C. and 60% humidity.

Next, the polyether amide imide resin (A) is uniformly dissolved in tetrahydrofuran so that the solid content is 50 parts by weight, and is dip-coated on the conductive elastic layer of the charging member,
After drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member. A resin layer was similarly provided on the aluminum sheet, and the volume resistance was measured.

As shown in FIG. 4, this charging member is used as a positive development type copying machine PC.
-20 (manufactured by Canon) In place of the primary corona charger, it is driven to rotate with the electrophotographic photoreceptor, and the primary charging voltage superimposes DC voltage -750V and AC peak-to-peak voltage 1500V,
The potential measurement of dark potential and bright potential of the electrophotographic photosensitive member and the image were examined.

 The results are shown in Table 1.

Further, the charging member was examined in a low-temperature and low-humidity state at a temperature of 15 ° C. and a humidity of 10%. It was shown to.

Example 2 In the same manner as in Example 1, a conductive elastic layer of a charging member was prepared.

Next, the polyether amide imide resin (B) is uniformly dissolved in tetrahydrofuran so that the solid content is 50 parts by weight, and is dip-coated on the conductive elastic layer of the charging member,
After drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Example 3 In the same manner as in Example 1, a conductive elastic layer of a charging member was prepared.

Next, the polyether amide imide resin (C) is uniformly dissolved in tetrahydrofuran so that the solid content is 50 parts by weight, and is dip-coated on the conductive elastic layer of the charging member,
After drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Example 4 In the same manner as in Example 1, a conductive elastic layer of a charging member was prepared.

Next, the polyether amide imide resin (D) is uniformly dissolved in tetrahydrofuran so that the solid content is 50 parts by weight, and is dip-coated on the conductive elastic layer of the charging member,
After drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Comparative Example 1 In the same manner as in Example 1, a conductive elastic layer of a charging member was prepared.

Next, 10 parts by weight of nylon 6-66-10-12
The resin was dissolved in 90 parts by weight, dip-coated on the conductive elastic layer of the charging member, and after drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Comparative Example 2 A conductive elastic layer of a charging member was prepared in the same manner as in Example 1.

Next, 10 parts by weight of methoxymethylated nylon-6 (methoxymethylation rate: 25%) was dissolved in 90 parts by weight of methanol, dip-coated on the conductive elastic layer of the charging member, and dried to a thickness of 200 μm. And a roller-shaped charging member was manufactured.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Comparative Example 3 In the same manner as in Example 1, a conductive elastic layer of a charging member was prepared.

Next, 8 parts by weight of a polyester polyol (Nipporan 121, manufactured by Nippon Polyurethane Co., Ltd.) and 2 parts by weight of toluylene diisocyanate are dissolved in 90 parts by weight of n-butanol, and then dip-coated on the conductive elastic layer of the charging member. Work,
After drying, a resin layer having a thickness of 200 μm was provided to produce a roller-shaped charging member.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

Comparative Example 4 A conductive elastic layer of a charging member was prepared in the same manner as in Example 1.

Next, 10 parts by weight of silicon RTV rubber was dissolved in 90 parts by weight of toluene, and the solution was applied by dip coating on the conductive elastic layer of the charging member, and after drying, a resin layer having a thickness of 200 μm was provided. Was manufactured.

 This was evaluated in the same manner as in Example 1 and shown in Table 1.

As can be seen by comparing Examples 1, 2, 3, and 4 with Comparative Examples 1 and 2, the present invention can prevent the occurrence of image defects of wavy fog caused by hardening of the resin layer at low temperature and low humidity.

Further, as can be seen by comparing Examples 1, 2, 3, and 4 with Comparative Examples 3 and 4, fusion between the charging member and the photoconductor can be prevented, and the generation of a horizontal streak image can be suppressed.

Example 5 Hereinafter, characteristics as a transfer charger were examined.

 A photoconductor was produced in the same manner as in Example 1.

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
A part by weight was melted and kneaded, and formed into a φ30 × 240 mm through a stainless shaft of φ8 × 260 mm at the center to provide a conductive elastic layer of a roller-shaped transfer charging member.

The volume resistance of this transfer charging member was set at 22 ° C and 60% humidity.
It is 4 × 10 ⁴ Ω · cm when measured in the environment.

Next, the polyether amide imide resin (A) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, and is dip-coated on the conductive elastic layer of the transfer charging member. A 100 μm resin layer was provided to produce a roller-shaped transfer charging member. A resin layer was similarly provided on an aluminum sheet.

This transfer charging member was attached in place of the transfer corona charger of the positive development type copying machine PC-20 (manufactured by Canon), and DC-500 V was applied for transfer charging, and the state of the image and the transfer charging member was examined.

 The results are shown in Table 2.

Further, Table 2 shows the image and the state of the transfer charging member when the transfer charging member was attached to a positive development type copying machine at a low temperature and low humidity of 15 ° C. and a humidity of 10%.

Example 6 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, the polyether amide imide resin (B) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the transfer charging member, and dried. A 100 μm resin layer was provided to produce a roller-shaped transfer charging member.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Example 7 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, the polyether amide imide resin (C) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the transfer charging member, and dried. A 100 μm resin layer was provided to produce a roller-shaped transfer charging member.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Example 8 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, the polyether amide imide resin (D) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the transfer charging member, and dried. A 100 μm resin layer was provided to produce a roller-shaped transfer charging member.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Comparative Example 5 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, 10 parts by weight of nylon-6-66-10-12 are dissolved in 90 parts by weight of methanol, and dip-coated on the conductive elastic layer of the transfer charging member. After drying, a resin layer having a thickness of 100 μm is formed. And a roller-shaped transfer charging member was manufactured.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Comparative Example 6 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, 10 parts by weight of methoxymethylated nylon-6 (25% by weight of methoxymethylation) is dissolved in 90 parts by weight of methanol, dip-coated on the conductive elastic layer of the transfer charging member, and dried. A 100 μm resin layer was provided to produce a roller-shaped transfer charging member.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Comparative Example 7 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, 8 parts by weight of a polyester polyol (Nipporan 121, manufactured by Nippon Polyurethane) and 2 parts by weight of toluylene diisocyanate are dissolved in 90 parts by weight of n-butanol, and dip-coated on the conductive elastic layer of the transfer charging member. After drying, a resin layer having a thickness of 100 μm was provided to produce a roller-shaped transfer charging member.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

Comparative Example 8 In the same manner as in Example 5, a conductive elastic layer of a transfer charging member was prepared.

Next, 10 parts by weight of silicon RTV rubber was dissolved in 90 parts by weight of toluene, and the resultant was applied by dip coating on the conductive elastic layer of the transfer charging member, and after drying, a resin layer having a thickness of 100 μm was provided. The members for manufacture were manufactured.

 This was evaluated in the same manner as in Example 5, and is shown in Table 2.

As can be seen from Examples 5, 6, 7, and 8 and Comparative Examples 5 and 6, in the present invention, even under low temperature and low humidity, high image quality can be maintained without lowering of density or wavy fog.

Furthermore, as can be seen from Examples 5, 6, 7, and 8 and Comparative Examples 7 and 8, in the present invention, the transfer charging member does not fuse with the photoconductor and also does not fuse with the toner. Can be used without generation.

Example 9 Hereinafter, characteristics as a static eliminator were examined.

 A photoconductor was produced in the same manner as in Example 1.

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
A part by weight was melt-kneaded and molded on a 2 mm × 260 mm stainless plate at the center to a free length of 10 mm × 240 mm as shown in FIG. 3 to provide a conductive elastic layer of a blade-shaped charging member. The volume resistance of the charge removing member is set to a temperature of 22 ° C and a humidity of 60.
It is 4 × 10 ⁴ Ω · cm when measured in a% environment.

Next, the polyether amide imide resin (A) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 50 parts by weight, and is dip-coated on the conductive elastic layer of the charge removing member. A 100 μm resin layer was provided to produce a blade-shaped member for static elimination and charging. A resin layer was similarly provided on the aluminum sheet, and the volume resistance was measured.

This static elimination charging member is installed in place of the pre-exposure static eliminator of the positive development type copier PC-20 (manufactured by Canon). For static elimination, an AC peak-to-peak voltage of 1000 V is applied. The state of the members for use was examined.

 The results are shown in Table 3.

Furthermore, the volume resistance of the resin layer of the charge-eliminating member in a low-temperature and low-humidity state at a temperature of 15 ° C. and a humidity of 10%, and the image and the state of the charge-eliminating member when the charge-eliminating member is attached to the positive development type copying machine The results are shown in Table 3.

Example 10 In the same manner as in Example 9, a conductive elastic layer of a member for discharging and charging was prepared.

Next, the polyether amide imide resin (B) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the charge removing member, and dried. A 100 μm resin layer was provided to produce a blade-shaped member for static elimination and charging.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Example 11 In the same manner as in Example 9, a conductive elastic layer of a charge removing member was prepared.

Next, the polyether amide imide resin (C) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the charge removing member, and dried. A 100 μm resin layer was provided to produce a blade-shaped member for static elimination and charging.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Example 12 In the same manner as in Example 9, a conductive elastic layer of a member for discharging and charging was prepared.

Next, the polyether amide imide resin (D) is uniformly dissolved in tetrahydrofuran so as to have a solid content of 40 parts by weight, dip-coated on the conductive elastic layer of the charge removing member, and dried. A 100 μm resin layer was provided to produce a blade-shaped member for static elimination and charging.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Comparative Example 9 In the same manner as in Example 9, a conductive elastic layer of a member for discharging and charging was prepared.

The charge removing member was used without providing a resin layer.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Comparative Example 10 In the same manner as in Example 9, a conductive elastic layer of a member for discharging and charging was prepared.

Next, 10 parts by weight of methoxymethylated nylon-6 (methoxymethylation rate 25%) was dissolved in 90 parts by weight of methanol, dip-coated on the conductive elastic layer of the charge removing member, and dried. A 100 μm resin layer was provided to produce a blade-shaped member for static elimination and charging.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Comparative Example 11 In the same manner as in Example 9, a conductive elastic layer of a charge removing member was prepared.

Next, 8 parts by weight of a polyester polyol (Nipporan 121, manufactured by Nippon Polyurethane) and 2 parts by weight of toluylene diisocyanate are dissolved in 90 parts by weight of n-butanol, and dip-coated on the conductive elastic layer of the member for static elimination and charging. After drying, a resin layer having a thickness of 100 μm was provided to produce a blade-shaped member for static elimination and charging.

 This was evaluated in the same manner as in Example 9 and shown in Table 3.

Comparative Example 12 The static elimination was performed by pre-exposure without using the static elimination charging member of the present invention, and this was evaluated in the same manner as in Example 9 and shown in Table 3.

As can be seen by comparing Examples 9, 10, 11, 12 and Comparative Examples 9, 11, in the present invention, fusion between the charging member and the photoreceptor is prevented, and the occurrence of horizontal streak-like image defects is prevented. .

Further, as can be seen by comparing Examples 9, 10, 11, and 12 with Comparative Example 10, stable static elimination performance is exhibited even at low temperature and low humidity, and the material of the present invention can suppress image defects.

In Comparative Example 12, the static elimination performance was low in the conventional pre-exposure type static elimination, and the residual potential was likely to remain at low temperature and low humidity, causing a background fog defect.

[Effects of the Invention] As is clear from the above results, by using the charging member of the present invention, the adhesion to the electrophotographic photoreceptor is low and the flexibility is high. Less toner stains. In particular, stable potential characteristics and image characteristics can be obtained even under low temperature and low humidity.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 and FIG. 2 are cross-sectional views in the central axis direction of a roller-shaped charging member, FIG. 3 is a cross-sectional view of a blade-shaped charging member, FIG. 4, FIG. The figure is a sectional view of the electrophotographic apparatus. 1a: conductive support, 1b: conductive sheet metal 2: conductive elastic layer, 3: resin layer 4: protective layer, 5: resin powder 6: charging member, 7: image exposure means 8: developing means 9: Corona charger for transfer charging 10: Cleaning means 11: Pre-exposure means, 12: Electrophotographic photoreceptor 14: Corona charger for primary charging 15: Charging member for transfer charging 16: Charging member for static elimination charging

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03G 15/02 G03G 15/16 G03G 15/08 B32B 27/34

Claims (5)

(57) [Claims] 1. A charging member having a conductive elastic layer on a conductive support, comprising: a resin layer containing a polyetheramideimide resin on the conductive elastic layer. 2. A charging member according to claim 1, wherein said charging member contacts said electrophotographic photosensitive member to charge said photosensitive member. 3. The charging member according to claim 1, wherein a DC voltage and an AC voltage are superimposed as an applied voltage to primary charge the electrophotographic photosensitive member. 4. The charging member according to claim 1, wherein a DC voltage is used as an applied voltage or a DC voltage and an AC voltage are superimposed to transfer a developer from an electrophotographic photosensitive member to a member to be transferred. . 5. The charging member according to claim 1, wherein the electrophotographic photosensitive member is neutralized by using an AC voltage as an applied voltage.