JPH0467071A - Electrifying member - Google Patents

Abstract

PURPOSE:To allow the stable supply of high-grade images by providing a resin layer contg. a polyether amide imide resin on a conductive elastic layer. CONSTITUTION:The basic form of this member is to adopt the three-layerd constitution consisting in providing the conductive elastic layer 2 on a conductive base 1 and providing the resin layer 3 contg. the polyether amide imide resin on the elastic layer 2. Further, a protective layer 4 may be provided on the surface of the electrifying member in order to protect the electrifying member. Since the electrifying member having the resin layer contg. such polyether amide imide resin has the low adhesiveness to an electrophotographic sensitive body and has resilience as well, the images having high quality are obtd. and the contamination with toners is lessened. The stable potential characteristics and image characteristics are obtd. in this way particularly at and under a low temp. and low humidity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a charging member, and particularly to a charging member used for primary charging, transfer charging, and static elimination charging in electrophotography.

[Prior Art] The charging process in an electrophotographic process using an electrophotographic photoreceptor has conventionally applied a high voltage (DC5) to a metal wire.
~8 kV) is applied, and charging is performed by the generated corona. However, with this method, when corona occurs, corona products such as ozone and NO change the surface of the photoreceptor, causing image blurring and deterioration, and wire dirt affects image quality, resulting in white spots and black spots in one image. There were problems such as streaks. On the other hand, in terms of electric power, the current flowing toward the photoreceptor is
The amount was only 30%, and most of it flowed to the shield plate, making it ineffective as a charging means.

In order to compensate for these deficiencies, many direct charging methods have been researched and proposed (Japanese Unexamined Patent Publications No. 57178267, No. 104351/1983, No. 58/4
0566, JP-A-58-139156, JP-A-58-150975, etc.). However, in reality, even if the photoreceptor is charged by the contact charging method as described above, the surface of the photoreceptor is not uniformly charged at each part, and uneven charging occurs. For example, in the reversal development method, even if a process below photoimage exposure is applied to a photoconductor with spotty charging unevenness, the output image will be a spotty black dot image corresponding to the spotty charging unevenness, whereas in the regular development method, the output image will be a spotty black dot image corresponding to the spotty charging unevenness. In contrast to the unevenness, the image becomes a speckled white dot image, making it impossible to obtain a high-quality image.

Further, although there are many proposals for the direct charging method, there is no market experience at all. The reason for this is the uniformity of charging,
Examples of such problems include the occurrence of discharge dielectric breakdown of the photoreceptor due to direct voltage application. For example, in the case of a cylindrical photoreceptor, one breakdown point due to discharge dielectric breakdown has the disadvantage that the entire charge in the axial direction flows to the breakdown point and is no longer charged.

[Problems to be Solved by the Invention] In order to prevent this dielectric breakdown, a method of forming a resin layer on the surface has also been reported. (JP-A-1205180, JP-A-1-211779) However, these materials also have large fluctuations in resistance under low temperature and low humidity conditions, have unstable charging properties, and cannot be used in contact with an organic photoreceptor. This had defects such as the resins on the surfaces of the charging member becoming compatible with each other and sticking to each other.

Therefore, it is an object of the present invention to provide a charging device that can solve the above-mentioned drawbacks and stably supply high-quality images without causing spot fog due to non-uniform charging or image defects due to discharge dielectric breakdown of the photoreceptor. The goal is to provide parts.

[Means for Solving the Problems] That is, the present invention provides a charging member having a conductive elastic layer on a conductive support, which has a resin layer containing a polyetheramide-imide resin on the conductive elastic layer. This is a charging member characterized by the following.

The present invention will be explained in more detail below.

As shown in FIG. 1, the charging member of the present invention includes a conductive elastic layer 2 provided on a conductive support la, and a resin layer 3 containing polyetheramide-imide resin on the elastic layer 2.
The basic form is a three-layer structure with .

The polyether amide imide resin used as the resin layer of the present invention is composed of trimellidic acid or its reactive acid derivatives, such as trimellidic anhydride, trimellidic anhydride chloride, and the general formula (1) % formula % (wherein R3-R4 is Hydrogen atom: Alkyl group such as methyl, ethyl, propyl, 1so-propyl, butyl, sec-butyl: Alkoxy group such as methoxy, ethoxy: Or halogen atom such as chlorine, bromine, R5, Rs
is a hydrogen atom: a substituted or unsubstituted alkyl group such as methyl, ethyl, trifluoromethyl, trichloromethyl, etc., or an alkenyl group such as a vinyl group), and an aromatic diamine having an ether bond represented by a solution polymerization method (for example, JP 44-19274, JP 49-4077, JP 42-15637, JP 57-14
No. 622), precipitation polymerization method (for example, Japanese Patent Publication No. 1983-
44719), a non-aqueous dispersion polymerization method (for example, U.S. Pat. No. 4,427.822), a melt polymerization method (Japanese Patent Publication No. 40-8910), etc., by condensation polymerization. be able to. In view of cost, a solution polymerization method in which trimellidic anhydride and diamine are subjected to condensation polymerization in the presence of a dehydration catalyst such as phosphoric acid is preferred.

-V It is preferable to use a total amount of 90 to 130 mol % of trimellidic acid or a reactive acid derivative thereof, particularly 100 mol % or approximately 100 mol %, based on the aromatic diamine having an ether bond represented by formula (1). It is preferable to use %.

In the present invention, the aromatic diamine having an ether bond represented by formula (I) is 2,2-bis[
4-(4-aminophenoxy)phenylcobroban, 2
．． 2-bis[3-methyl-4(4-aminophenoxy)
phenyl]propane, 2,2-bis[3-bromo-4-
(4-aminophenoxy)phenyl]propane, 2,2
-bis[3ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-propyl-4(4
-aminophenoxy)phenylconitane.

2.2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[ 3-5ec-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 1-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)phenylpropane, 2.2-bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]propane, 1.
1-bis[4-(4-aminophenoxy)phenylconitane, 1.1-bis[3-methyl-4-(4-aminophenoxy)phenylconitane, 1.1-bis[3-chloro-4-(4-amino Phenoxy) phenylconitane, 1
．． 1-bis[3-bromo-4-(4-aminophenoxy)phenylconitane, 1,1-bis[3-ethyl-4-
(4-aminophenoxy)phenylconitane, 1.1-
Bis[3-propyl-4-(4-aminophenoxy)phenylconitane, 1,1-bis[3-isopropyl-4
-(4-aminophenoxy)phenylconitane, 1.1
-bis[3-butyl-4-aminophenoxy)phenylconitane, 1,1-bis(3-5ec-butyl-4-(
4-aminophenoxy)phenylconitane, 1.1-bis[3-methoxy-4-(4-aminophenoxy)phenylconitane, 1.1-bisF3-ethoxy4-(4-
aminophenoxy)phenylconitane, 1,1-bis[
3,5-dimethyl-4-(4-aminophenoxy)phenylconitane, 1,1-bis[3,5-dichloro-4-
(4-aminophenoxy)phenylconitane, 1.1-
Bis[3,5-dibromo-4-(4-aminophenoxy)phenylconitane, 1,1-bis[3,5-dimethoxy-4-(4-aminophenoxy)phenylconitane,
1.1-bis[3-chloro-4-(aminophenoxy)
-5-methylphenylconitane, bis[4-(4-aminophenoxy)phenylcomethane, bis[3-methyl-
4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-4-(4-aminophenoxy)phenylcomethane, bis[3-bromo-4-(4-aminophenoxy)phenylcomethane, bis[ 3-ethyl-4-(4
-aminophenoxy)phenylcomethane, bis[3-propyl-4-(4-aminophenoxy)phenylcomethane, bis[3-isopropyl-4-(4-aminophenoxy)phenylcomethane, bis[3-butyl- 4-(4
-aminophenoxy)phenylcomethane, bis[3-5
ee-Butyl 4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-4-(4-aminophenoxy)phenylcomethane, bis[3-ethoxy-4-(
4-aminophenoxy)phenylcomethane, bis[3,
5-dimethyl-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dichloro-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dibromo-4-(4-amino phenoxy) phenylcomethane,
Bis[3,5-dimethoxy-4-(4-aminophenoxy)phenylcomethane, 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 1-propane,
3.3-bis[4-(4-aminophenoxy)phenyl]pentane, 1.1-bis[4-(4-aminophenoxy)phenyl]bropane, 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 1-propane, 1.1.1.3.3.3-hexafluoro2.2-bis[3,5-dibromo-4(4
-aminophenoxy)phenyl 1-propane, 1.1.1
．． 3.3.3-hexachloro-2,2-bis[3,5-
Dibromo4-(4-aminophenoxy)phenyl 1-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)phenylcobutane, 2,2-bis[3-methyl-4-(4 -aminophenoxy)phenylcobutene, 2
．． 2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl 1-butane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenylcobutane, 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 desired, mixtures of the above diamines can be used.

Furthermore, in the present invention, known diamines such as 4.4'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl sulfone, 4. 4′-benzophenone diamine, metaphenylene diamine, 4.4°-di(4-aminophenoxy) phenyl sulfone, paraphenylene diamine, 4,4′-di(3-aminophenoxy) phenyl sulfone, 3.3
'-diaminodiphenylsulfone, metaphenylenediamine, 1,3-bis(4-aminophenoxy)benzene, and the repeating unit represented by the example and the formula (Il
, ) (where m is a number in the range of 1 to 100) and the like can be used together with at least one diaminosiloxane. The ratio of these diamines to the total diamines is preferably 30 mol% or less. If this proportion exceeds 30 mol%, it is not preferable because it will have a negative effect on the solubility of the resin. The polyether amide imide polymer thus obtained is considered to be a polymer in which repeating units represented by formula (II) are bonded to each other as appropriate. However, in the mathematical formula (n) and the general formula (nl), A represents a benzene ring, B represents a residue of any of the above diamines excluding the amino group, and -
When the repeating unit of formula (II) and the repeating unit of general formula (III) are bonded, one B is the other N
is combined with

Unlike conventional polyamide-imide resins, these specific polyetheramide-imide resins are soluble in general-purpose organic thermal media with relatively low boiling points, such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclohexanone, and 4-methylcyclohexanone. It has the advantage that the coating liquid can be easily adjusted and the coating film can be dried at low temperatures and in a short time. Moreover, the obtained resin layer is also hard and tough.

Furthermore, 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 are preferred. Binder resins in the resin layer include acrylic resins such as polymethyl methacrylate and polybutyl methacrylate, polyvinyl butyral, polyvinyl acetal, polyarylate, polycarbonate,
Examples include phenoxy resin, polyvinyl acetate, and polyvinylpyridine.

Conventional charging members have surfaces made of rubber or polyurethane, so if they come into contact with an electrophotographic photoreceptor, the photoreceptor and charging member may stick together, or if the surface is hard, wrinkles may occur. This caused image defects.

On the other hand, the charging member having a resin layer containing the polyetheramide-imide resin of the present invention has low adhesion to the electrophotographic photoreceptor and is flexible, so it provides high-quality images and eliminates toner stains. There is little variation in the volume resistivity of the resin layer even under low temperature and low humidity conditions, and it can be used as a stable charging member.

The thickness of the resin layer is 5 to 500 μm, especially 20 to 200 LL.
A range of m is preferred.

The volume resistivity of the resin layer is preferably in the range of 106 to 10'2 Ω·cm. Further, as shown 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. The volume resistance of the elastic layer is 0° to 101Ω・cm,
In particular, a range of 102 to 1010 Ω·cm is preferable. As the elastic layer 2, metals such as aluminum, iron, and copper, conductive polymers such as polyacetylene, polypyrrole, and polythiophene, and rubber or plastic elastomer treated to be conductive by dispersing carbon, metal, etc., or the surface of rubber or plastic elastomer may be used. A laminate coated with metal or other conductive material can be used. Moreover, this elastic layer 2 may have a multilayer structure with separate functions as required. As the conductive support 1a, iron,
Copper, stainless steel, etc. can be used.

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 insoluble resin powder 5 may be mixed therein to control the conductivity and the 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 the conductive sheet metal 1b, and a resin layer 3
will be established.

Further, a protective layer may be provided.

The charging member may have any shape such as a roller shape or a blade shape, but a roller shape is preferable in terms of uniform charging.

Electrophotographic photoreceptors basically have a structure in which a photosensitive layer is provided on a conductive support. As the four-electrode support, materials whose support itself is conductive can be used, such as aluminum, aluminum alloy, stainless steel, chromium, titanium, etc. In addition, aluminum, aluminum alloy, indium oxide-tin oxide alloy, etc. The above-mentioned conductive support or plastic has a layer formed by vacuum deposition, a support in which plastic or paper is impregnated with conductive particles (e.g. carbon black, tin oxide particles, etc.) together with a suitable binder, or a conductive binder. It is possible to use plastics that have

A subbing layer having barrier and contact functions can also be provided between the conductive support and the photosensitive layer.

The subbing layer can be formed from casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane, gelatin, aluminum oxide, or the like. The thickness of the undercoat layer is preferably 5 um or less, preferably 0.5 to 3 LIIl. In order for the undercoat layer to perform its function, it is desirable that the undercoat layer has a thickness of 10'Ω·cm or more.

The photosensitive layer is formed, for example, by coating a photoconductor such as an organic photoconductor, amorphous silicon, selenium, etc. together with a binder if necessary, or by vacuum deposition. Furthermore, when using an organic photoconductor, a photosensitive layer consisting of a combination of a charge generation layer that generates charge carriers upon exposure to light and a charge transport layer that has the ability to transport the generated charge carriers can also be effectively used.

The charge generating layer may be formed by depositing one or more charge generating materials such as azo pigments, quinone pigments, quinone anine pigments, perylene pigments, indigo pigments, bisbenzimidazole pigments, phthalocyanine pigments, and quinacridine pigments, or by depositing a suitable material. It can be dispersed with a binder (or without a binder) and formed by coating.

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

The thickness of the charge generation layer is 0.01 to 15μ, preferably 0.
．． The weight ratio of the charge generation layer to the binder is 10:1-1:20.

The solvent used in the paint for the charge generation layer is selected based on the solubility and dispersion stability of the resin and charge transport material used, and examples of organic solvents include alcohols, sulfoxides, ethers, esters, and aliphatic halogenated solvents. Hydrocarbons or aromatic compounds can be used.

Coating can be done by dip coating method, spray coating method,
This can be done using a coating method such as a Mayer bar coating method or a blade coating method.

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

Examples of binders used in 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, and epoxy. resin,
Polyester, alkyd resin, polycarbonate, polyurethane or two of the repeating units of these resins
copolymers containing one or more, such as styrene-butadi\ene copolymers, styrene-acrylonitol copolymers,
Examples include styrene-maleic acid copolymer. It can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene.

The thickness of the charge transport layer is 5 to 50μ■, preferably 8 to 2O
LLm, and the weight ratio of charge transport material and binder is 5:
The ratio is about 1 to 1:5, preferably about 3:1 to 1.3. The coating method described above can be used for coating.

Furthermore, since dyes, pigments, organic charge transport substances, etc. are generally sensitive to ultraviolet rays, ozone, stains caused by oil, metals, etc., a protective layer may be provided as necessary.An electrostatic latent image is formed on this protective layer. In order to form a surface resistivity of 10”Ω
The above is desirable.

The protective layer of the photoreceptor is made of polyvinyl butyral, polyester, polycarbonate, acrylic resin, methacrylic resin,
It can be formed by dissolving a resin such as nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-acrylic acid copolymer, styrene-acrylonitrile copolymer, etc. in a suitable organic solvent on the photosensitive layer and drying it. . At this time, the thickness of the protective layer is generally in the range of 0.05 to 20 μm.

This 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. This apparatus includes a primary charging member 6, an image exposure means 7, a developing means 8. A corona charger 9 for transfer charging, a cleaning means 10, and a pre-exposure means 11 are arranged.

A voltage (for example, 200 V or more or more than 2000
A pulsating current voltage (which is a superimposition of a DC voltage of V or less and an AC voltage of a peak-to-peak voltage of 4000 V or less) is applied to the electrophotographic photoreceptor 1.
2, the surface of the document is charged, and the image on the document is image-exposed onto the photoreceptor by the image exposure means 7 to form an electrostatic latent image. Next, by attaching the developer in the developing means 8 to the photoreceptor, the electrostatic latent image on the photoreceptor is developed (visualized), and the developer on the photoreceptor is transferred to a corona charger for transfer charging. 9 transfers the developer onto a transfer member 13 such as paper, and a cleaning means 10 collects the developer remaining on the photoreceptor without being transferred to the paper during transfer.

Although an image can be formed by such an electrophotographic process, if residual charges remain on the photoreceptor, - Before performing the next electrophotography, the photoreceptor is exposed to light by the pre-exposure means 11 to remove the residual charges. It is better to eliminate static electricity.

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 corona charger 14 for primary charging, an image exposure means 7, a developing means 8, a charging member 15 for transfer charging, and a cleaning means 1O1 pre-exposure means 11 are arranged on the circumferential surface of an electrophotographic photoreceptor 12. .

A voltage (for example, a DC voltage of 400 to 100 O
V) can be applied to transfer the developer on the electrophotographic photoreceptor to a transfer member such as paper.

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

A voltage (for example, an AC peak-to-peak voltage of 500 to 500
zooov> can be applied to eliminate the charge on the electrophotographic photoreceptor.

By applying the charging member of the present invention to an electrophotographic photoreceptor having a photosensitive layer containing an organic photoconductor, which easily deteriorates in terms of mechanical strength and chemical stability, its characteristics can be clearly exhibited. can do.

In the present invention, the method for installing the charging member in contact with the photoreceptor is not limited to a specific method.
Any method of movement such as rotation in the same direction as the photoreceptor or in the opposite direction can be used. Furthermore, it is also possible to cause the charging member to function as a developer cleaning device on the photoreceptor.

Regarding the voltage applied to the charging member and the application method in the direct charging of the present invention, it depends on the specifications of each electrophotographic device, but in addition to the method of instantly applying the desired voltage, there are also methods for protecting the photoreceptor. A method can be adopted in which the applied voltage is increased stepwise, or in the case of applying a superimposed alternating current on a direct current, a method is applied in which the voltage is applied in the order of direct current (direct current, φ alternating current, or alternating current).

When the charging member of the present invention is used for primary charging of an electrophotographic device, it is necessary to apply a DC voltage and an AC voltage to the electrophotographic photoreceptor in the image pressure area.

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

Furthermore, in the present invention, processes such as image exposure, development, and cleaning can be performed using any method known in the field of electrostatic photography, and are not limited to specific methods such as the type of developer. The charging member of the present invention is applicable not only to copying machines but also to laser printers, CRT printers,
It can also be used in electrophotographic applications such as electrophotographic plate making systems and facsimile machines having receiving means for receiving image information from remote terminals.

[Example] Next, the present invention will be explained in detail based on the present example, but the present invention is not limited thereto.

First, four types of polyetheramide-imide resin materials and synthesis methods used in the resin layer are shown below.

0 Synthesis of polyether amide imide resin iA) Heavy trimellidic acid anhydrous propane N-methylpyrrolidone 30 Phosphoric acid aqueous solution 0. '3C phosphoric acid content: 85%) The above ingredients were stirred into a four-lobe flask equipped with a thermometer, stirrer, nitrogen inlet tube, and moisture meter, and the temperature was raised to 160°C while passing nitrogen gas. . The temperature was gradually raised to 205°C while distilled water was removed from the system, and the reaction proceeded in a temperature range of 205 to 210''C.

The end point of the reaction was controlled by Gardnall viscosity, and a polyetheramide-imide resin with a reduced viscosity (dimethylformamide, 0.5 g/di, 30° C., hereinafter the same) of 0.41 (di/g) was obtained. The obtained polyetheramide-imide resin solution was diluted with N-methylpyrrolidone to a concentration of about 25% by weight, and the droplets were dropped into water that had been strongly stirred with a mixer to form a solid polyetheramide-imide resin. was recovered. After washing this solid resin thoroughly with hot water,
Washed by boiling with plenty of water. After filtering this, 150℃
The mixture was dried in a hot air dryer for 6 hours to obtain a powdered polyetheramide-imide resin fAl.

0 polyetheramide imide resin fB) using the same components as the synthetic resin A, using the same equipment, and performing the same operations, except that the reaction end point was controlled by Gardner viscosity, and the reduced viscosity was 0.69 (di/ g) Powdered polyether amide imide resin fBl was obtained.

Synthesis weight of 0 polyether amide imide resin fcl
Parts by weight Trimelic acid anhydrous water 102.2-Bis[4-(4-20 aminophenoxy)phenyl] Propane N-methylpyrrolidone 30 Phosphoric acid aqueous solution 03 (phosphoric acid content 85
%) The above ingredients were placed in a four-lobe flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a moisture meter while stirring, and the temperature was raised to 160'C while nitrogen gas was passed through. The temperature was gradually raised to 205°C while removing distilled water from the system, and the reaction proceeded in the temperature range of 205 to 210"C. The end point of the reaction was controlled by Gardner viscosity, and the reduced viscosity [ Dimethylformamide, 0.5 g/dl, 30°C, the same applies hereinafter) A polyetheramide imide resin of 0.43 (di/g) was obtained.The obtained polyetheramide imide resin solution was diluted with N-methylpyrrolidone to a This solution was diluted to % by weight and poured into water that was strongly stirred with a mixer to recover solid polyetheramide-imide resin.After washing this solid resin thoroughly with hot water,
Washed by boiling with plenty of water. After filtering this, 150℃
The mixture was dried in a hot air dryer for 6 hours to obtain a powdered polyetheramide-imide resin 1c).

Using the same components as the synthetic resin A of the 0 polyetheramide imide resin fDl, the same operation was carried out using the same equipment, but the reaction end point was controlled by Gardner viscosity, and the reduced viscosity was 0.68 (di/g ) powder polyether amide imide resin FD+ was obtained.

Example 1 As a conductive support, 60φ×2 with a wall thickness of 0.50111
A 6011I11 aluminum cylinder was prepared.

4 parts of copolymerized nylon (trade name: M8000, manufactured by Toshi ■) and 4 parts of type 8 nylon (trade name: Shikamite 5003, manufactured by Dainippon Ink ■) were mixed with 50 parts of methanol.
The solution was dissolved in 50 parts of n-butanol and dip coated onto the above support to form a subbing layer with a thickness of 0.6 μm.

10 parts of a disazo pigment with the following structural formula, and polyvinyl butyral resin (trade name: Kosurek B)
10 parts of M2 (manufactured by Building Block Chemical), 12 parts of cyclohexanone
It was dispersed for 10 hours in a sand mill with 0 parts. 30 parts of methyl ethyl ketone was added to the dispersion and coated on the undercoat layer to form a charge generation layer with a thickness of 0.15 μm.

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

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
Melt and knead the weight part and form a φ8 piece in the center as a conductive support.
ψ20X 2 through the stainless steel shaft of X 260mm
A conductive elastic layer of a roller-shaped charging member was provided.

The volume resistance of the conductive elastic layer of this charging member is determined at a temperature of 22
℃, humidity 60%, 1j, 3 x 10'Ω・
cm.

Next, polyether amide imide resin fAI was uniformly dissolved in tetrahydrofuran so that the solid content was 50 parts by weight, and the solution was dip coated onto the tetraelectric elastic layer of the charging member, and after drying, the film thickness was 200 μl. A roller-shaped charging member was manufactured by providing a resin layer of.

A resin layer was similarly provided on an aluminum sheet, and the volume resistance was measured.

This charging member is connected to a normal development type copying machine PC as shown in Fig. 4.
-2Of Canon) - Installed in place of the next corona charger and rotated as a result of the electrophotographic photoreceptor.

- Wide charging voltage was measured using a DC voltage of -750V and an AC peak-to-peak voltage of 1500V, and the bright potential of the electrophotographic photoreceptor was measured and the image was examined.

The results are shown in Table 1.

Furthermore, we investigated the volume resistance of the resin layer of the charging member under low temperature and low humidity conditions of 15°C and 10% humidity, as well as the potential characteristics and images when this charging member was attached to a normal development type copying machine. Shown in 1.

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

Next, polyether amide imide resin + Bl was uniformly dissolved in tetrahydrofuran so that the solid content was 50 parts by weight, and dip coating was applied onto the conductive elastic layer of the charging member, and after drying, a film thickness of 200 am was obtained. A resin layer was provided to produce a roller-shaped charging member.

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

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

Next, polyether amide imide resin FCL was uniformly dissolved in tetrahydrofuran so that the solid content was 50 parts by weight, and dip coating was applied onto the tetraelectric elastic layer of the charging member, with a film thickness of 200 μm after drying. A roller-shaped charging member was prepared by providing a resin layer of blue color.

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

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

Next, polyetheramide imide resin FD+ is uniformly dissolved in tetrahydrofuran so that the solid content is 50 parts by weight, and dip coating is applied onto 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 is shown in Table 1.

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

Next, 10 parts by weight of Nylon Toro 6-10-12 was dissolved in 90 parts by weight of methanol, and the solution was dip-coated on the conductive elastic layer of the charging member to form a resin layer with a thickness of 200 μι after drying. A roller-shaped charging member was manufactured.

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

Comparative Example 2 A conductive stretchable 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, and the solution was dip coated onto the conductive elastic layer of the charging member, and after drying, the film thickness was 200 μm. A resin layer (2) was provided to produce a roller-shaped charging member.

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

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

Next, 8 parts by weight of Tuboran 121° (manufactured by Nippon Polyurethane) and 2 parts by weight of toluylene diisocyanate were dissolved in 90 parts by weight of n-butanol in polyester polyol, and the solution was dip coated onto the conductive elastic layer of the charging member. A resin layer having a thickness of 200 μm after drying was provided to produce a roller-shaped charging member.

This was evaluated in the same manner as in Example 1 and is 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 silicone 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 with a film thickness of 200 μ- was provided, and a resin layer for roller-shaped charging was applied. The parts were manufactured.

This was evaluated in the same manner as in Example 1 and is 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 image defects such as wavy fog caused by hardening of the resin layer at low temperatures and low cleanliness.

Furthermore, as can be seen by comparing Examples 1, 2, and 3.4 with Comparative Examples 3 and 4, it is possible to prevent fusion between the charging member and the photoreceptor, and to suppress the occurrence of horizontal streak images.

Example 5 Below, the characteristics as a transfer charger were investigated.

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

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
The weight parts were melted and kneaded, and a stainless steel shaft of φ8×2601111 mm was passed through the center and formed into a size of φ30×240 mm, and a conductive elastic layer of a roller shape transfer charging member was provided.

The volume resistance of this transfer charging member was determined at a temperature of 22°C and a humidity of 60°C.
% environment, it is 4 x 10'Ω・Cll1.

Next, polyether amide imide resin (Al) was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip coated on the conductive elastic layer of the transfer charging member, and after drying, the film thickness was 100 μI. A resin layer was provided on the aluminum sheet to produce a roller shape transfer charging member.A resin layer was similarly provided on the aluminum sheet.

This transfer charging member was attached in place of the transfer corona charger of a normal development type copying machine PC-20 (manufactured by Canon), a direct current of -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, the image and the state of the transfer charging member when the transfer charging member was attached to a normal development type copying machine under a low temperature condition of 15° C. and 10% humidity were investigated and are shown in Table 2.

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

Next, polyether amide imide resin fBl was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and dip coating was applied onto the conductive elastic layer of the transfer charging member, with a film thickness of 100 μl after drying. A roller shape transfer charging member was manufactured by providing a resin layer of.

This was evaluated in the same manner as in Example 5 and shown in Table 1.

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

Next, polyetheramide imide resin fc) was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip coated onto the conductive elastic layer of the transfer charging member, and after drying, the film thickness was 100 μm. A porcelain resin layer was provided to produce a roller shape transfer charging member.

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

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

Next, polyether amide imide resin tDl was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip coated onto the conductive elastic layer of the transfer charging member, and after drying, the film thickness was 100 μII+. A resin layer was provided to produce a roller shape transfer charging member.

This was evaluated in the same manner as in Example 5 and shown in Table 1.

Comparative Example 5 A conductive stretchable layer of a transfer charging member was prepared in the same manner as in Example 5.

Next, 10 parts by weight of nylon-6-66-10-12 was dissolved in 90 parts by weight of methanol, and the solution was dip coated onto the conductive elastic layer of the transfer charging member, and after drying, the resin had a film thickness of 00 um. A layer was provided to produce a roller shape transfer charging member.

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

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

Next, 10 parts by weight of methoxymethylated nylon-6 (methoxymethylation rate 25%) was dissolved in 90 parts by weight of methanol, and the solution was dip coated onto the conductive elastic layer of the transfer charging member, and after drying, the film thickness was A resin layer of 100 μm was provided to produce a roller shape transfer charging member.

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

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

Next, 8 parts by weight of Tuboran 121 (manufactured by Nippon Polyurethane) and 2 parts by weight of toluylene diisocyanate were dissolved in 90 parts by weight of n-butanol in polyester polyol, and the solution was dip coated onto the soil of the conductive elastic layer of the transfer charging member. , film thickness after drying] 00 um (7) A resin layer was provided to produce a roller shape transfer charging member.

This was evaluated in the same manner as in Example 5 and shown in Table 1.

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

Next, 10 parts by weight of silicone RTV rubber was dissolved in 90 parts by weight of toluene, and the solution was dip coated on the conductive elastic layer of the transfer charging member, and after drying, a resin layer with a film thickness of 100 μm was provided, and the roller shape transfer charging was performed. We manufactured parts for this purpose.

This was evaluated in the same manner as in Example 5 and shown in Table 1.

As can be seen from Examples 5.6 and 7.8 and Comparative Examples 5 and 6, the present invention can maintain high image quality without causing a decrease in density or wavy fog even under low temperature and low humidity conditions.

Furthermore, as can be seen from Examples 5, 6, 7.8 and Comparative Examples 7 and 8, in the present invention, the transfer charging member does not fuse with the photoconductor, nor does it fuse with the toner, so defects may occur in the photoconductor or charging member. Can be used without generation.

Example 9 Below, we investigated its characteristics as a static eliminator.

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

Next, conductive carbon 5 was added to 100 parts by weight of chloroprene rubber.
Melt and knead the weight parts and place 2+IIIIIIX260m in the center.
Free length 10mmX as shown in Figure 3 on a stainless steel plate of
It was molded to have a length of 240 mm, and a conductive elastic layer of a blade-shaped charging member was provided. When the volume resistance of this charge eliminating static charge member is measured in an environment of temperature 22℃ and humidity 60%, it is 4
10' Ω·clTl.

Next, the polyether amide imide resin fA) was uniformly dissolved in tetrahydrofuran so that the solid content was 50 parts by weight, and the solution was dip-coated on the conductive elastic layer of the static elimination/charging member, and after drying, the film thickness was A resin layer of 100 g+m was provided to produce a blade-shaped static elimination/charging member. A resin layer was similarly provided on the aluminum sheet, and the volume resistance was measured.

This charge-eliminating member was installed in place of the pre-exposure charge eliminator of a normal development type copying machine PC-20 (manufactured by Canon), and an AC peak-to-peak voltage of 1000 V was applied to remove the charge. The condition of the parts used was examined.

The results are shown in Table 3.

Furthermore, the volume resistance of the resin layer of the static eliminating charging member, the image of this static eliminating charging member attached to a normal development type copying machine, and the state of the static neutralizing charging member in a low temperature and low humidity condition of 15°C and 10% humidity were investigated. The results are shown in Table 3.

Example 10 In the same manner as in Example 9, a conductive elastic layer of a static elimination/charging member was prepared.

Next, polyether amide imide resin fBl was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip-coated on the conductive elastic layer of the static elimination/charging member, and after drying, a film thickness of 1100 LL was obtained. A resin layer was provided, and a blade-shaped static elimination/charging member was manufactured.

This was evaluated in the same manner as in Example 9 and shown in Table 1.

Example 11 In the same manner as in Example 9, a conductive elastic layer of a static elimination/charging member was prepared.

Next, polyether amide imide resin tc+ was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip coated onto the conductive elastic layer of the static elimination/charging member, and after drying, the film thickness was 100 μm. A blade-shaped static eliminator charging member was manufactured by providing a resin layer.

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

Example 12 In the same manner as in Example 9, a conductive elastic layer of a static elimination/charging member was prepared.

Next, polyether amide imide resin fDl was uniformly dissolved in tetrahydrofuran so that the solid content was 40 parts by weight, and the solution was dip coated onto the conductive elastic layer of the static elimination/charging member, and after drying, the film thickness was 10C). A resin layer of u+1 was provided, and a blade-shaped static elimination/charging member was manufactured.

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 charge eliminating member was prepared.

The static elimination/charging member was used as it was without providing a resin layer.

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

Comparative Example 10 In the same manner as in Example 9, a conductive elastic layer of a static elimination/charging member was prepared.

Next, 10 parts by weight of methoxymethylated nylon-6 (methoxymethylation rate 25%) was dissolved in 90 parts by weight of methanol, and the solution was dip-coated on the conductive elastic layer of the static electricity removal charging member, and after drying, the film thickness was A 100 μι resin layer was provided to produce a blade-shaped static elimination/charging member.

This was evaluated in the same manner as in Example 9, and the results are shown in Table 3. Comparative Example 11 A conductive elastic layer of a static elimination charging member was prepared in the same manner as in Example 9.

Next, 8 parts by weight of Tuboran 121 (manufactured by Nippon Polyurethane) and 2 parts by weight of toluylene diisocyanate were dissolved in 90 parts by weight of n-butanol in polyester polyol, and the solution was applied by dip coating onto the conductive elastic layer of the static eliminating charge member. After drying, a resin layer having a thickness of 100 .mu.m was provided to produce a blade-shaped static elimination/charging member.

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

Comparative Example 12 Static electricity was removed by pre-exposure without using the static eliminating/charging member of the present invention, and this was evaluated in the same manner as in Example 9, and the results are shown in Table 1.

As can be seen by comparing Examples 9, 10, 11.12 and Comparative Example 9.11-, the present invention prevents fusion between the charging member and the photoreceptor and prevents the occurrence of image defects in the form of horizontal stripes. There is.

Moreover, as can be seen by comparing Examples 9, 10, 11.12 and Comparative Example 10, stable static elimination performance was exhibited even under low temperature and low humidity, and the material of the present invention can suppress image defects.

In Comparative Example 12, the static elimination performance of the conventional pre-exposure type static elimination was low, and residual potential was likely to remain at low temperature and low humidity, causing soil burr defects.

[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;
Since it is also flexible, it provides high-quality images with less toner stains. In particular, stable potential characteristics and image characteristics can be obtained even under low temperature and low humidity conditions.

[Brief explanation of the drawing]

Figures 1 and 2 are sectional views in the central axis direction of a roller-shaped charging member, Figure 3 is a sectional view of a blade-shaped charging member, and Figures 4, 5, and 6 are cross-sectional views of an electrophotographic device. It is a diagram. 1a. Conductive support lb = Conductive sheet metal 2: Conductive elastic layer 3: FM fat layer 4: Protective layer 5. Resin powder 6: Charging member 7: Image exposure means 8 Developing means 9: Transfer charging corona Charger 10/cleaning means 11: pre-exposure means 12 electrophotographic photoreceptor 14, -
Next issue: Corona charger 15 for charging and charging member 16 for transfer charging: Charging member for static electricity removal agent Patent attorney Jo Taira Yamashita Figure 1 Figure 4 Figure 2 Figure 3

Claims (1)

[Claims] (1) A charging member having a conductive elastic layer on a conductive support, characterized by having a resin layer containing polyetheramide-imide resin on the conductive elastic layer. Charging member. (2) The charging member according to claim 1, wherein the charging member contacts an electrophotographic photoreceptor to charge the photoreceptor. (3) The charging member according to claim 1, wherein the electrophotographic photoreceptor is primarily charged by superimposing a DC voltage and an AC voltage as applied voltages. (4) The charging member according to claim 1, wherein the developer is transferred from the electrophotographic photoreceptor to the transfer member by using a DC voltage as the applied voltage or by superimposing a DC voltage and an AC voltage. (5) The charging member according to claim 1, wherein the electrophotographic photoreceptor is neutralized using an alternating current voltage as the applied voltage.