JPH0511483A - Polyamide resin and electrophotographic sensitive body using same - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body having stable potential characteristics and giving a stable image in any environment independently of temp. and humidity by using specified polyamide resin. CONSTITUTION:In this electrophotographic sensitive body having a photosensitive layer on the electric conductive substrate with a middle layer in-between, the middle layer contains polyamide resin having a unit component represented by formula I, wherein R1, is optionally substd. alkyl, R2, is optionally substd. alkylene and n is an integer of >=1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin and an electrophotographic photoreceptor using the same, and more particularly to improvement of an intermediate layer provided between a support and a photosensitive layer.

[0002]

2. Description of the Related Art Generally, in a Carlson type electrophotographic photosensitive member, the stability of the dark portion potential and the light portion potential is stable when a charge-exposure is repeated to form an image having a constant image density and no fog. Has become important.

Therefore, it has an intermediate function of improving charge injection from the support to the photosensitive layer, improving adhesion between the support and the photosensitive layer, improving coatability of the photosensitive layer, and covering defects on the support. It has been proposed to provide a layer between the support and the photosensitive layer.

Further, there has been proposed one having a laminated structure in which a photosensitive layer is functionally separated into a charge generation layer and a charge transport layer. Generally, the charge generation layer is provided as an extremely thin layer, for example, about 0.5 μm. Therefore, defects, stains, deposits or scratches on the surface of the support cause nonuniformity of the film thickness of the charge generation layer. If the film thickness of the charge generation layer is not uniform, the sensitivity of the photosensitive member will be uneven. Therefore, it is required to make the charge generation layer as uniform as possible.

From the above, it has been proposed to provide an intermediate layer having a function as a barrier layer, an adhesive layer and a function of covering defects on the support between the charge generation layer and the support. There is.

Conventionally, as a layer provided between the photosensitive layer and the support, polyamide (JP-A-46-47344, JP-A-52-25638, JP-A-58-95351),
Polyester (JP-A-52-20836, JP-A-54)
No. 26738), polyurethane (JP-A-49-100)
44, JP-A-53-89435, casein (JP-A-55-103556), polypeptide (JP-A-53-53435).
-48523), polyvinyl alcohol (JP-A-52)
-100240), polyvinylpyrrolidone (JP-A-4
8-30936), vinyl acetate-ethylene copolymer (JP-A-48-26141), maleic anhydride polymer (JP-A-52-10138), polyvinyl butyral (JP-A-57-90639, JP 58-1
No. 06549), quaternary ammonium salt-containing polymers (JP-A-51-126149, JP-A-56-60448).
No.), ethyl cellulose (JP-A-55-143564)
No.) etc. are known to be used.

[0007]

However, in the electrophotographic photosensitive member using the above-mentioned material as the intermediate layer, the resistance of the intermediate layer changes due to the change in temperature and humidity, so that the temperature changes from low temperature and low humidity to high temperature and high humidity. It was difficult to always obtain stable potential characteristics and image quality with respect to the environment.

For example, when the photoconductor is repeatedly used under low temperature and low humidity where the resistance of the intermediate layer becomes high, the electric potential remains in the intermediate layer, and the bright portion potential and the residual potential increase, causing fog in the copied image or reversal. When such a photoconductor is used in an electrophotographic printer for development, there are problems that the image density becomes low and a copy having a constant image quality cannot be obtained.

Further, under high temperature and high humidity, the barrier function is lowered due to the lower resistance of the intermediate layer, the carrier injection from the support side is increased, and the dark part potential is lowered. For this reason,
Under high temperature and high humidity, the density of the copied image may become light,
When such a photoconductor is used in an electrophotographic printer that performs reversal development, there is a problem that black spot defects (black spots) and fogging tend to occur in an image.

Therefore, an object of the present invention is to provide an electrophotographic photosensitive member which can obtain stable potential characteristics and images in all environments from low temperature and low humidity to high temperature and high humidity.

Another object of the present invention is to provide an electrophotographic photosensitive member which can form an excellent image without defects by forming an intermediate layer capable of sufficiently covering the defects on the support.

[0012]

That is, according to the present invention, a polyamide resin having a unit component represented by the following general formula (I), a photosensitive layer is formed on a conductive support through an intermediate layer. An electrophotographic photosensitive member having the general formula (I), wherein the intermediate layer contains a polyamide resin having a unit component represented by the following general formula (I).

[0013]

[Chemical 3] (In the formula, R ₁ represents a substituted or unsubstituted alkyl group, R ₂ represents a substituted or unsubstituted alkylene group, and n represents an integer of 1 or more), and an electrophotographic apparatus including the photoconductor, It is a facsimile.

The contents of the present invention will be described in detail below.

In the general formula (I), the alkyl group represented by R ₁ includes a methyl group, an ethyl group, a propyl group and the like, and the alkylene group represented by R ₂ includes a methylene group, an ethylene group and a propylene group. , An isopropylene group, and the like. These alkyl group and alkylene group may have a substituent such as a halogen atom, an aryl group such as a phenyl group, and an alkoxy group.

The polyamide resin of the present invention is one in which hydrogen of the amide group of the polyamide resin used for the main chain is replaced by a substitution reaction to obtain a modified polyamide resin having a unit component represented by the general formula (I).

As the polyamide resin constituting the main chain of the modified polyamide used in the present invention, 6,11,12,
Nylon resins such as 66,610; and copolymer nylon resins containing the above components; N-alkoxymethylated, N
-Alkylated nylon resin; nylon resin containing an aromatic component and the like.

Further, the modified polyamide used in the present invention can be used by cross-linking in consideration of the solvent resistance of the coating material for the photosensitive layer. Crosslinking is usually carried out by heat treatment after forming a coating film using an epoxy compound, a melamine compound or the like. When N-alkoxymethylated nylon resin is used as the polyamide component, self-crosslinking by heating is carried out using an acid catalyst such as citric acid, adipic acid, tartaric acid, maleic acid, hypophosphorous acid, etc. without using a crosslinking agent. A crosslinked product can also be formed by

The main chain component of the polyamide resin used in the present invention is, for example,

[0020]

[Chemical 4] And the like, or a copolymer having two or more of these structures as a unit component. Specific examples of such a main chain component will be shown.

[0021]

[Table 1] Next, examples of the modified polyamide resin actually used in the present invention will be shown.

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7] The electrophotographic photoreceptor of the present invention contains the above-mentioned modified polyamide resin in the intermediate layer, so that environmental changes such as increase in residual potential under low temperature and low humidity and decrease in dark area potential due to decrease in barrier function under high temperature and high humidity. Can be prevented.

The modified polyamide resin according to the present invention does not change much in volume resistance under each environment, and when this resin is used as an intermediate layer, an electrophotographic photoreceptor having less environmental change can be obtained. The resistance of a normal polyamide resin decreases by about three digits when it is exposed to high temperature and high humidity rather than room temperature and normal humidity, but the modified polyamide resin shows almost no change.

The reason why the environmental change of the modified polyamide resin is small is not clear, but the following structural factors are considered. (1) By attaching a side chain, it becomes easier to become amorphous and network than a linear polymer when forming a coating film, it is easy to hold a conductive substance such as water or ions retained inside, and the film formability becomes good, Hole-like coating film defects are unlikely to occur. (2) Water and ionic substances are easily adsorbed by the polar group of the side chain. Also, the adhesiveness of the film is improved.

From the above two points, the resistance does not increase even at low temperature and low humidity, and the network structure formed in an amorphous state prevents excessive incorporation of water molecules into the inside of the coating film and improves the film forming property. Therefore, it is considered that the resistance does not suddenly decrease even under high temperature and high humidity.

The modified polyamide used in the present invention can be synthesized by reacting a polyamide as a raw material with a polyaldehyde and an alcohol to replace hydrogen of an amide group.

Next, specific synthesis examples of the modified polyamide of the present invention will be shown.

Synthesis Example 1 (Exemplified Compound [1]) 50 g of 6-nylon resin was mixed with 250 g of formic acid and 25 g of acetic anhydride.
It was put in 0 g of a mixed solvent and dissolved by stirring. Paraformaldehyde (15 g) and 2-methoxyethanol (35 g) were added thereto, and the mixture was heated to 60 ° C. and reacted for 5 hours. Next, the reaction solution was cooled to room temperature, then poured into 5 liters of acetone and reprecipitated and filtered to obtain a white reaction product. This product was washed by stirring in a large amount of water, filtered and dried under reduced pressure at 40 ° C. and 10 to 20 mmHg, and 50.7 g of methoxyethoxymethylated 6-nylon resin (methoxyethoxymethyl group substitution rate 31%). Got

The intermediate layer of the present invention may be composed of the above-mentioned modified polyamide alone, or may be composed of a system to which other resins, additives and conductive substances are added, if necessary. Examples of other resins added here include copolymer nylon, N
-Examples include polyamides such as alkoxymethylated nylon, polyesters, polyurethanes, polyureas, and phenolic resins. Examples of additives include titanium oxide,
Examples thereof include powders such as alumina and resins, surfactants, leveling agents, coupling agents and the like.

When a conductive substance is used, aluminum,
Metal powders such as copper, nickel and silver, metal foils and short metal fibers; conductive metal oxides such as antimony oxide, indium oxide and tin oxide; polypyrrole, polyaniline,
Polymer conductive materials such as polymer electrolytes; carbon fibers, carbon black, graphite powder; or conductive powders whose surfaces are coated with these conductive substances.

In the present invention, the thickness of the intermediate layer is set in consideration of electrophotographic characteristics and defects on the support, and can be set to about 0.1 to 50 μm, but usually 0.5. ~ 5 μm, 1 to 30 when a conductive substance is added
μm is preferred. The intermediate layer coating is dip coating,
It can be performed by a method such as spray coating or roll coating.

Further, in the present invention, a second intermediate layer containing a resin as a main component may be provided on the intermediate layer, if necessary, such as controlling the barrier property.

Examples of the resin material used for the second intermediate layer include polyamide, polyester, polyurethane, polyurea, and phenol resin in addition to the modified polyamide described above.

The thickness of this second intermediate layer is 0.1-5 μm.
m is preferable and it is applied by the same method as the above-mentioned intermediate layer.

In the present invention, the photosensitive layer may be a single layer type or a laminated structure type in which the charge generating layer and the charge transporting layer are functionally separated.

The charge generation layer of the laminated structure type photoreceptor is an azo pigment such as Sudan Red or Diane Blue, a quinone pigment such as pyrene quinone or anthanthrone, a quinocyanine pigment, a perylene pigment, an indigo pigment such as indigo or thioindigo, an azurenium salt pigment, Copper phthalocyanine,
A charge generating substance such as a phthalocyanine pigment such as oxytitanium phthalocyanine is dispersed in a binder resin such as polyvinyl butyral, polystyrene, polyvinyl acetate, acrylic resin, polyvinylpyrrolidone, ethyl cellulose, and cellulose acetate butyrate, and the dispersion is dispersed as described above. It can be formed by coating on the intermediate layer. The thickness of such a charge generation layer is 5 μm or less, preferably 0.1 μm or less.
It is 05-2 micrometers.

The charge transport layer provided on the charge generation layer has a main chain or side chain of biphenylene, anthracene, pyrene,
A polycyclic aromatic compound having a structure such as phenanthrene,
It is formed using a coating liquid in which a nitrogen-containing cyclic compound such as indole, carbazole, oxadiazole, or pyrazoline, a charge transporting substance such as a hydrazone compound, or a styryl compound is dissolved in a resin having film-forming properties. The reason for forming in this way is that the charge transporting substance generally has a low molecular weight,
This is because the film forming property itself is poor.

Examples of the resin having such a film forming property include polyester, polycarbonate, polymethacrylic acid ester, polystyrene and the like.

The thickness of the charge transport layer is 5 to 40 μm, preferably 10 to 30 μm.

Further, in the present invention, an organic photoconductive polymer layer such as polyvinylcarbazole or polyvinylanthracene; a selenium vapor deposition layer, a selenium-tellurium vapor deposition layer, an amorphous silicon layer, etc. can be used as the photosensitive layer.

In the present invention, in addition to the above layer structure, the photosensitive layer may have a layer structure in which a charge generation layer is provided on the charge transport layer.

On the other hand, the support used in the present invention may be any support as long as it has conductivity. For example, a metal such as aluminum, copper, chromium, nickel, zinc or stainless is molded into a drum or sheet. A metal foil such as aluminum or copper laminated on a plastic film, aluminum, indium oxide, tin oxide, etc. deposited on a plastic film, or a conductive substance applied alone or with an appropriate pine resin to make it conductive. Examples include layer-provided metals, plastic films, and paper.

As the conductive substance used for this conductive layer, metal powder such as aluminum, copper, nickel and silver,
Metal foils and short metal fibers; conductive metal oxides such as antimony oxide, indium oxide, and tin oxide; polymer conductive materials such as polypyrrole, polyaniline, and polymer electrolytes;
Carbon fiber, carbon black, graphite powder; organic and inorganic electrolytes; or conductive powder whose surface is coated with these conductive substances.

As the binder resin used in the conductive layer, polyamide, polyester, acrylic resin,
Thermoplastic resins such as polyamino resin ester, polyvinyl acetate, polycarbonate, polyvinyl formal, polyvinyl butyral, polyvinyl alkyl ether, polyalkylene ether, polyurethane elastomer, and thermosetting resins such as thermosetting polyurethane, phenol resin, epoxy resin, etc. Can be mentioned.

The mixing ratio of the conductive substance and the binder resin is
It is about 5: 1 to 1: 5. This mixing ratio is determined in consideration of the resistance value of the conductive layer, surface properties, coating suitability, and the like.

When the conductive substance is powder, a ball mill,
A mixture is prepared and used by a conventional method using a roll mill, a sand mill or the like.

Further, as other additives, a surfactant, a silane coupling agent, a titanate coupling agent, a silicone oil, a silicone leveling agent or the like may be added.

FIG. 1 shows a schematic structural example of a general transfer type electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

In the figure, reference numeral 1 is a drum type photosensitive member of the present invention as an image bearing member, which is rotationally driven around an axis 1a in a direction of an arrow at a predetermined frequency. The photosensitive member 1 is uniformly charged at its peripheral surface by a charging unit 2 at a predetermined positive or negative potential in the course of its rotation, and then at an exposure unit 3 an optical image exposure L (slit exposure Laser beam scanning exposure). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor.

Then, the electrostatic latent image is developed with toner by the developing means 4 and the toner developed image is rotated by the transfer means 5 between the photoconductor 1 and the transfer means 5 from a paper feeding portion (not shown). The images are sequentially transferred onto the surface of the transfer material P that has been synchronized and fed.

The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to the image fixing and printed out as a copy.

After the image transfer, the surface of the photosensitive member 1 is cleaned by the cleaning means 6 to remove the residual toner after transfer, and is further discharged by the pre-exposure means 7 to be repeatedly used for image formation.

As the uniform charging means 2 for the photosensitive member 1, a corona charging device is generally widely used. In addition, the transfer device 5
Corona transfer means are also widely used. The electrophotographic apparatus is configured by integrally combining a plurality of constituent elements such as the photoconductor, the developing unit, and the cleaning unit described above as an apparatus unit, and the unit is configured to be detachable from the apparatus body. May be. For example, the photoconductor 1
Alternatively, the cleaning unit 6 and the cleaning unit 6 may be integrated into one unit, and may be detachably configured by using a guide unit such as a rail of the apparatus main body. At this time, the above device unit may be provided with a charging unit and / or a developing unit.

When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L is reflected light or transmitted light from an original, or an original is read out and converted into a signal, and a laser beam is scanned or an LED is emitted by this signal. This is performed by driving the array, driving the liquid crystal shutter array, or the like.

When used as a printer for a facsimile, the optical image exposure L becomes an exposure for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The entire controller 11 is CP
It is controlled by U17. The read data from the image reading unit 10 is transmitted to the partner station through the transmission circuit 13. The data received from the partner station is sent to the printer 19 through the receiving circuit 12. The image memory 16 stores predetermined image data. The printer controller 18 controls the printer 19. 14 is a telephone.

The image information received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, then decoded by the CPU 17, and sequentially stored in the image memory 16. Is stored. When the image information of at least one page is stored in the memory 16, the image recording of that page is performed. The CPU 17 reads out one page of image information from the memory 16 and sends the decoded one page of image information to the printer controller 18. Upon receiving the image information of one page from the CPU 17, the printer controller 18 controls the printer 19 to record the image information of the page.

The CPU 17 is receiving the next page while the printer 19 is recording.

The image is received and recorded as described above.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines, but also in laser beam printers, C
RT printer, LED printer, liquid crystal printer,
It can be widely used in electrophotographic application fields such as laser plate making.

[0066]

EXAMPLES The present invention will be described in more detail with reference to specific examples. Parts in the examples indicate parts by weight.

Example 1 50 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 25 parts of phenol resin,
20 parts of methyl cellosolve, 5 parts of methanol and 0.002 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3,000) are dispersed for 2 hours in a sand mill using φ1 mm glass beads for a conductive layer. A paint was prepared.

Aluminum cylinder (φ30 mm × 2
60mm), and apply the above coating by dip coating,
It was dried for 0 minutes to form a conductive layer having a film thickness of 20 μm.

Next, 5 parts of the above-mentioned exemplary polymer [I] was dissolved in 95 parts of methanol to prepare a coating material for the intermediate layer.

This coating material was applied onto the conductive layer by dip coating,
It was dried at 90 ° C. for 10 minutes to form an intermediate layer having a film thickness of 0.6 μm.

Next, the structural formula

[0072]

[Chemical 5] 3 parts of disazo pigment, 2 parts of polyvinylbenzal (benzalization rate 75%, weight average molecular weight 13,000) and 35 parts of cyclohexanone were dispersed for 8 hours in a sand mill using φ1 mm glass beads, and then methyl ethyl ketone (MEK) 60 Was added to prepare a charge generation layer dispersion liquid. This dispersion is dip coated on the above intermediate layer,
It was dried at 0 ° C. for 20 minutes to form a charge generation layer having a film thickness of 0.2 μm.

Next, the structural formula

[0074]

[Chemical 6] Of styryl compound and 10 parts of polycarbonate (weight average molecular weight of 46,000) were added to dichloromethane 20 parts.
Part, and dissolved in a mixed solvent of 40 parts of monochlorobenzene,
This solution is applied onto the above charge generation layer by dip coating at 120 ° C.
And dried for 60 minutes to form a charge transport layer having a thickness of 18 μm.

The electrophotographic photosensitive member thus produced was attached to a reversal development type laser printer in which the process of charging-exposure-developing-transfer-cleaning was repeated in a cycle of 2.0 seconds, and it was stored at room temperature and normal humidity (23 ° C). , 50% R
H) and under high temperature and high humidity (30 ° C., 85% RH) environment, the electrophotographic characteristics were evaluated.

As a result, as shown in Table 1, in the photoconductor of Example 1, the difference between the dark portion potential (V _D ) and the light portion potential (V _L ) was large, and sufficient potential contrast was obtained.
The dark area electricity (V _D ) was stable even under high temperature and high humidity, and a good image without black spot defects (black spots) and fog was obtained.

Examples 2 to 5 Examples of polymers for intermediate layer coating polymers [2], [3], [5],
Other than using the modified polyamide resin of [6],
Electrophotographic photosensitive members were manufactured in the same manner as in Example 1, and were set as Examples 2 to 5, respectively.

When these photoreceptors were evaluated in the same manner as in Example 1, in all cases, the dark potential (V _D ) was stable even under high temperature and high humidity, and there were no black spot defects (black spots) and no fog. An image was obtained.

The results are shown in Table 1.

Comparative Example 1 Instead of the modified polyamide resin described above in the paint for the intermediate layer,
N-methoxymethylated 6 nylon (weight average molecular weight 12
Comparative Example 1 was carried out in the same manner as in Example 1 except that the amount of the electrophotographic photosensitive member was 10,000, and the methoxymethyl group substitution rate was 33%.

When this photoreceptor was evaluated in the same manner as in Example 1, the chargeability deteriorated under high temperature and high humidity, and the dark area potential (V _D ) decreased. As a result, black spot defects appeared on the image. (Black spots) have started to occur.

The results are shown in Table 1.

[0083]

[Table 8] Example 6 Exemplified polymer

[9] 5 parts were dissolved in 95 parts methanol to prepare a coating material for the intermediate layer.

An aluminum cylinder (φ
30mm x 360mm) and apply it by dip coating at 100 ° C for 2
It was dried for 0 minutes to form an intermediate layer having a film thickness of 1.2 μm.

Next, 4 parts of oxytitanium phthalocyanine pigment and polyvinyl butyral (butyralization ratio 68
%, 34,000 parts by weight average molecular weight of 24,000 and 34 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 10 hours, and then 60 parts of tetrahydrofuran (THF) was added to prepare a dispersion liquid for a charge generation layer. This dispersion is dip-coated on the above intermediate layer,
And dried for 15 minutes to form a charge generation layer having a thickness of 0.15 μm.

Next, the styryl compound 7 used in Example 1
Parts and polycarbonate (weight average molecular weight 59.00)
0) 10 parts was dissolved in a mixed solvent of 15 parts of dichloromethane and 45 parts of monochlorobenzene, the solution was applied onto the above charge generation layer by dip coating, and dried at 120 ° C. for 60 minutes,
A charge transport layer having a film thickness of 25 μm was formed.

The electrophotographic photosensitive member thus manufactured was mounted on a copying machine in which the process of charging-exposure-developing-transfer-cleaning was repeated in a cycle of 0.6 seconds.

For this photoreceptor, low temperature and low humidity (15 ° C.,
When the electrophotographic characteristics were evaluated in an environment of 10% RH), as shown in Table 2, this photosensitive member had a large difference between the dark portion potential (V _D ) and the light portion potential ( _VL ) and was found to be sufficient. A potential contrast was obtained. Furthermore, when 1000 images were continuously output, a stable image was obtained with little increase in the light portion potential ( _VL ).

Examples 7-10 Exemplified Polymers for Intermediate Layer Coatings [10], [16], [2]
9] and [33], except that each modified polyamide resin was used, an electrophotographic photosensitive member was manufactured in the same manner as in Example 6, and Examples 7 to 10 were made.

When these photoconductors were evaluated in the same manner as in Example 6, all the photoconductors had a large difference between the dark portion potential (V _D ) and the light portion potential ( _VL ) and a sufficient potential contrast was obtained. In addition, even when 1000 images were continuously output, a stable image was obtained with a small increase in the bright part potential ( _VL ).

The results are shown in Table 2.

Comparative Example 2 Instead of the modified polyamide resin described above in the paint for the intermediate layer,
Alcohol-soluble copolymer nylon (weight average molecular weight 6
6,000) was used, and an electrophotographic photosensitive member was produced in the same manner as in Example 6, and was designated as Comparative Example 2.

When this photosensitive member was evaluated in the same manner as in Example 6, the light portion potential (V _L ) increased after continuous 1000 sheets were repeated, and fog was generated on the image.

The results are shown in Table 2.

[0095]

[Table 9] Example 11 25 parts of conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide, 20 parts of rutile type titanium oxide powder, 20 parts of the above-mentioned exemplary polymer [13], 20 parts of methanol, 10 parts of 2-propanol was dispersed for 4 hours in a sand mill using φ1 mm glass beads to prepare a coating material for the intermediate layer.

Aluminum cylinder (φ60mm × 26
0 mm), the above coating composition was applied by dip coating and dried at 160 ° C. for 30 minutes to form an intermediate layer having a film thickness of 16 μm.

Next, 5 parts of alcohol-soluble copolymer nylon (weight average molecular weight 66,000) was added to 95 parts of methanol.
15 parts at 90 ° C.
After drying for a minute, a second intermediate layer having a film thickness of 0.3 μm was formed.

Next, the structural formula

[0099]

[Chemical 7] 2 parts of disazo pigment, 1 part of polyvinyl butyral (butyralization rate 68%, weight average molecular weight 18,000) and 30 parts of cyclohexanone were dispersed in a sand mill using φ1 mm glass beads for 20 hours, and then 65 parts of methyl ethyl ketone (MEK) was added. To prepare a dispersion liquid for the charge generation layer. This dispersion is dip coated on the second intermediate layer,
It was dried at 0 ° C. for 20 minutes to form a charge generation layer having a film thickness of 0.2 μm.

Next, the structural formula

[0101]

[Chemical 8] 9 parts of hydrazone compound and 10 parts of polycarbonate (weight average molecular weight 46000) were added to 20 parts of dichloromethane.
Part, and dissolved in a mixed solvent of 40 parts of monochlorobenzene,
This solution is applied onto the above charge generation layer by dip coating at 120 ° C.
For 60 minutes to form a charge transport layer having a thickness of 23 μm.

The electrophotographic photosensitive member produced in this manner was attached to a copying machine in which the processes of charging-exposure-developing-transfer-cleaning were repeated in a cycle of 0.8 seconds.

For this photoreceptor, low temperature and low humidity (15 ° C.,
When electrophotographic characteristics were evaluated in an environment of 10% RH), as shown in Table 3, this photosensitive member had a large difference between the dark portion potential (V _D ) and the light portion potential ( _VL ) and was found to be sufficient. A potential contrast was obtained. Furthermore, when 1000 images were continuously output, a stable image was obtained with little increase in the light portion potential ( _VL ).

Example 12 An intermediate layer, a charge generation layer, and a charge transport layer were formed in the same manner as in Example 11 except that the second intermediate layer was not provided.
The electrophotographic photosensitive member of Example 12 was manufactured.

When this photosensitive member was evaluated in the same manner as in Example 11, the difference between the dark portion potential (V _D ) and the light portion potential ( _VL ) was large, sufficient potential contrast was obtained, and 1000 continuous sheets were obtained. Bright part potential ( _VL )
A stable image was obtained with little increase in

The results are shown in Table 3.

Comparative Examples 3 and 4 Example 11 was repeated except that a phenol resin was used in place of the modified polyamide of Example 11 in the intermediate layer paint containing conductive titanium oxide powder and rutile type titanium oxide powder.
Electrophotographic photosensitive members were manufactured in the same manner as in Nos. 1 and 12, and Comparative Examples 3 and 4 were made respectively.

When this photosensitive member was evaluated in the same manner as in Example 11, in Comparative Example 3, the bright portion potential ( _VL ) increased after repeating 1000 sheets continuously, and fog was generated on the image. . Further, in Comparative Example 4 in which the charge generation layer and the charge transport layer were directly provided on the intermediate layer, the barrier property of the intermediate layer was insufficient, and the charge injection from the support side was large and the dark part potential (V
_{Since D} ) was low, the potential contrast required for image formation could not be obtained.

The results are shown in Table 3.

[0110]

[Table 10] Example 13 (modified with HOCH ₂ CH ₂ OCH ₃ ) 100 g of 6-nylon, 3.76 g of methyl cellosolve, 80 g of paraformaldehyde in a 2 liter autoclave.
Was charged and heated and stirred at 120 ° C. to dissolve the raw material nylon.

Then, 25 g of methyl cellosolve to which 1 g of phosphoric acid was added was charged and reacted at 120 ° C. for 45 minutes. The reaction mixture was poured into water and allowed to stand overnight to take out the resin which solidified into a sticky shape, and was crushed. The pulverized product was repeatedly washed with alkali and further washed with water. The resin component taken out was air-dried, dissolved in 200 g of methanol, and the insoluble matter was filtered off,
The resin solution was poured into water, the solidified resin was crushed, and washed repeatedly with water until formaldehyde was not observed by the Schiff reagent.

80 g of dry resin was obtained. Denaturation rate 30%.

IR spectrum: 1050 to 1100 cm ^-1
(-COC-) ^13C -NMR spectrum (ppm): 78 (-N-CH)
_{2 O-) 65,68 (-O-CH} 2 -), 58 (-O-CH 3) Example _{14 (HO-CH 2 CH 2} -O-C 4 those modified with H ₉₎ 6- Nylon 100g , Paraformaldehyde 100
g, buttercellosolve 400 g (total amount) and phosphoric acid 2 g were used, and the reaction temperature was 140 ° C. and the reaction time was 1 hour. The same procedure as in Example 13 was carried out to obtain 75 g of a polyamide resin modified by 25%. . ¹³ C-NMR spectrum (pp
m): 60~70 (-O-CH 2 -) Example _{15 (HO-CH 2 CH 2} O-CH 2 CH 2 O-
Modified with C ₂ H ₅ ) 6-nylon 100 g, diethylene glycol monoethyl ether 300 g, paraformaldehyde 100 g,
The same procedure as in Example 13 was carried out except that 4 g of phosphoric acid was used, the reaction temperature was 130 ° C., and the reaction time was 1 hour, to obtain 85 g of a 15% -modified polyamide resin.

IR spectrum (cm ^-1 ): 1050 to ¹
100 (-COC-) ^13C -NMR spectrum (ppm): 65,68 (-O)
_{-CH 2 -), 14 (-CH} 3) Example 16

[0115]

[Chemical 9] 6-nylon 100g, paraformaldehyde 100
g, ethylene glycol monobenzyl ether 400
g and phosphoric acid 4 g were used, the reaction temperature was 160 ° C., and the reaction time was 2 hours.
80 g of 5% modified polyamide resin was obtained.

[0116]

[Chemical 10] Example 17 (HOCH ₂ CH ₂ OCH ₂ CH ₂ OC
H ₃₎ those modified with) one liter autoclave 6-nylon 100 g, diethylene glycol monomethyl ether 250 g, were charged paraformaldehyde 100 g, and heating and stirring to 130 ° C.. Next, a mixture of 25 g of diethylene glycol monomethyl ether and 4 g of phosphoric acid was charged, and the mixture was reacted at 130 ° C. for 60 minutes. Then, the content was poured into water and treated in the same manner as in Example 13 to give 15%.
95 g of modified polyamide resin was obtained.

IR spectrum: 1050 to 1100 cm
^-1 (-COC-) ^13C -NMR spectrum (ppm): 78 (-N-CH)
_{2 -) 65,68 (-O-CH} 2 -), 58 (-O-CH 3) by changing the environment were evaluated for surface resistivity and triboelectric charge quantity of the modified polyamide obtained in Example 13 to 17 . (* 1) (* 2) Surface resistivity (Ω) Friction charge (V) 23 ℃ / 55% rh 23 ℃ / 15% rh 23 ℃ / 55% rh 23 ℃ / 15% rh Example 13 4.2 × 10 ⁹ 5.1 × 10 ⁹ 0 0 14 2.6 × 10 ⁹ 9.8 × 10 ⁹ 0 0 15 3.7 × 10 ⁹ 2.1 × 10 ⁹ 0 0 16 1.5 × 10 ⁹ 2.2 × 10 ¹⁰ 0 0 17 3.5 × 10 ⁹ 2.0 × 10 ¹⁰ Comparative Example 5 4.5 × 10 ¹⁰ 1.2 × 10 ¹² 0 130 6 3.3 × 10 ¹³ 1.2 × 10 ¹⁴ 150 340 Comparative Example 5: Using methoxymethylated nylon 〃 6: 6,66-Using nylon * 1) JIS According to K6911. * 2) It shows the saturated charge amount under a load of 300 g.

[0118]

As can be seen from the above examples, the electrophotographic photosensitive member of the present invention is a polyamide having a unit component represented by the following general formula (I) in the intermediate layer between the support and the photosensitive layer. Resin general formula (I)

[0119]

[Chemical 11] (Wherein R ₁ represents a substituted or unsubstituted alkyl group, R ₂ represents a substituted or unsubstituted alkylene group, and n represents an integer of 1 or more). Stable potential characteristics and good images can be obtained in all environments even under humid conditions.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a general transfer type electrophotographic apparatus.

FIG. 2 is a block diagram of a facsimile using the electrophotographic apparatus as a printer.

[Explanation of symbols]

1 photoconductor 2 charging means 3 exposure section 4 developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyoshi Sakai             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation

Claims (6)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support through an intermediate layer, wherein the intermediate layer contains a polyamide resin having a unit component represented by the following general formula (I). An electrophotographic photoconductor characterized by the general formula (I): (In the formula, R ₁ represents a substituted or unsubstituted alkyl group, R ₂ represents a substituted or unsubstituted alkylene group, and n represents an integer of 1 or more). 2. The electrophotographic photosensitive member according to claim 1, wherein the intermediate layer contains a conductive substance. 3. The electrophotographic photosensitive member according to claim 1, wherein the conductive support has a support base and a conductive layer provided thereon containing a conductive substance and a binder resin. body. 4. An electrophotographic apparatus provided with the electrophotographic photosensitive member according to claim 1. 5. A facsimile equipped with the electrophotographic photosensitive member according to claim 1 and having a receiving means for receiving image information from a remote terminal. 6. A compound represented by the general formula (I): (In the formula, R ₁ represents a substituted or unsubstituted alkyl group, R ₂ represents a substituted or unsubstituted alkylene group, and n represents an integer of 1 or more). A polyamide resin having a unit component represented by: