JPH0772636A - Electrophotographic photoreceptor and electrophotographic device formed by using this electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To eliminate the crack of a charge transfer layer and the crystallization of a charge transfer material even if the electrophotographic photoreceptor is not used over a long period of time or even if the photoreceptor is provided with a protective layer by incorporating a specific triphenyl amine into a photosensitive layer. CONSTITUTION:This electrophotographic photoreceptor has a substrate and the photosensitive layer formed on this substrate. The triphenyl amine which has at least two pieces of alkyl groups and in which one of the alkyl groups is bonded to the position of meta with respect to a nitrogen atom is incorporated into the photosensitive layer. The photosensitive body 1 receives a uniform electrostatic charge of a prescribed positive or negative potential on its peripheral surface in the process of its rotation by electrostatic charging means 2 and thereafter, the photosensitive body is subjected to light image exposing L by an image exposing means. The electrostatic latent images successively formed in such a manner are then developed with toners by a developing means 4. These toner developed images are successively transferred onto the surfaces of recording materials P which are taken out between the photosensitive body 1 and a transfer means 5 synchronously with rotation of the photosensitive body 1 from a paper feed section by the transfer means 5 and are fed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member and an electrophotographic apparatus using this electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, selenium has been used as an electrophotographic photoreceptor.
Inorganic photoreceptors having a photosensitive layer containing zinc oxide, cadmium or the like as a main component have been widely used. Inorganic photoreceptors have problems such as difficulty in forming a photosensitive layer, poor plasticity, and high manufacturing cost. Further, the inorganic photoconductive material is generally highly toxic, and there are great restrictions in manufacturing and handling.

On the other hand, an organic photoconductor containing an organic photoconductive compound as a main component has many advantages such as supplementing the above-mentioned drawbacks of an inorganic photoconductor and has been attracting attention in recent years, and many proposals have been made so far. Some have been put to practical use.

As such an organic photoreceptor, poly-N is used.
An electrophotographic photoreceptor containing a charge transfer complex formed of a photoconductive polymer represented by vinylcarbazole and a Lewis acid such as 2,4,7-trinitro-9-fluorenone as a main component has been proposed. . These organic photoconductive compounds are superior to the inorganic photoconductive compounds in terms of lightness and film formability, but in terms of sensitivity, durability, stability due to environmental changes, etc., the inorganic photoconductive compounds are It is inferior to, and is not always satisfactory.

On the other hand, a function-separated type electrophotographic photosensitive member in which a charge generating function and a charge transporting function are shared by different substances, is remarkably improved in sensitivity and durability, which have been the drawbacks of conventional organic photosensitive members. Brought. Such a function-separated type photoreceptor has the advantages that the material selection range of the charge generating substance and the charge transporting substance is wide, and that an electrophotographic photoreceptor having desired characteristics can be prepared relatively easily.

As the charge generating substance, various kinds of azo pigments, polycyclic quinone pigments, cyanine dyes, squaric acid dyes, pyrylium salt dyes and the like have been conventionally known. Among them, many structures have been proposed for azo pigments in terms of high light resistance, high charge generation ability, easy material synthesis, and the like.

On the other hand, examples of the charge transport material include a pyrazoline compound disclosed in JP-B-52-4188 and JP-B-55.
-42380 and JP-A-55-52063, hydrazone compounds, JP-A-3-114058 and JP-A-5-53349, triphenylamine compounds, JP-A-54-151955 and JP-A-54-151955. 58
The stilbene compound disclosed in Japanese Patent Publication No. 198043 is known. Unlike the compounds used in the present invention, the above triphenylamine compounds did not have sufficient performance as charge transport materials.

[0008]

A member such as a cleaning blade is in contact with the photosensitive member. However, if the photosensitive member is not used for a long period of time with the cleaning blade or the like kept in contact with the photosensitive member, the charge transport layer is formed. A crack was generated in the film, a phenomenon in which the charge transport material was crystallized and phase separation was caused, which was a cause of image defects. Further, when the protective layer is provided for improving the durability, the charge transport layer may be adversely affected by the protective layer to cause cracks in the charge transport layer, or the charge transport material may be crystallized and phase-separated.

Further, in the reversal development method corresponding to the recent digitalization, since the primary charging and the transfer charging have opposite polarities, there occurs a so-called transfer memory in which the potential of the primary charging is different between when the transfer charging is performed and when it is not performed. The density unevenness on the image is very likely to appear.

An object of the present invention is to provide an electrophotographic photosensitive member which does not cause cracks in the charge transport layer and crystallize the charge transport material even when it is not used for a long period of time or a protective layer is provided. An object is to provide an electrophotographic apparatus using an electrophotographic photosensitive member.

An object of the present invention is to provide an electrophotographic photosensitive member having good sensitivity, stable electrophotographic characteristics even after repeated use, and less likely to cause transfer memory in the reversal development method, and the electrophotographic photosensitive member. To provide an electrophotographic apparatus using the.

[0012]

The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer formed on the support, has two alkyl groups, and contains one of the alkyl groups. One is that the photosensitive layer contains triphenylamine having at least two phenyl groups bonded at the position meta to the nitrogen atom.

The electrophotographic photoreceptor of the present invention comprises a support and a photosensitive layer formed on the support, and triphenylamine having at least two phenyl groups having three alkyl groups, It is contained in the photosensitive layer.

The electrophotographic apparatus of the present invention forms the electrostatic latent image by performing image exposure on the electrophotographic photosensitive member, charging means for charging the electrophotographic photosensitive member, and the charged electrophotographic photosensitive member. And an image exposing unit for developing the electrophotographic photosensitive member on which the electrostatic latent image is formed with a toner.

The electrophotographic photosensitive member of the present invention contains triphenylamine having at least two phenyl groups having two or three alkyl groups bonded to the photosensitive layer on the support. This triphenylamine is used as a charge transport material and is represented by the following general formula [1] according to the structural formula.

[0016]

[Outside 2]

In the general formula [1], Ar ₁ , Ar ₂ and Ar
₃ represents a phenyl group. Two or three alkyl groups are bonded as substituents to at least two phenyl groups of Ar _{1 to} Ar ₃ , respectively.

1 out of 2 or 3 alkyl groups
The alkyl groups are preferably in the meta position relative to the nitrogen atom. Particularly, in the case of a phenyl group having two alkyl groups, sufficient performance cannot be obtained unless one alkyl group is in the meta position with respect to the nitrogen atom.

Further, of the two or three alkyl groups, one alkyl group is in the meta position with respect to the nitrogen atom and one alkyl group is in the para position with respect to the nitrogen atom. It is preferable.

The alkyl group has 1 to 4 carbon atoms,
That is, a methyl group, an ethyl group, a propyl group, and a butyl group are preferable.

The preferred examples of triphenylamine used in the present invention are shown below.

[0022]

[Outside 3]

[0023]

[Outside 4]

[0024]

[Outside 5]

[0025]

[Outside 6]

[0026]

[Outside 7]

[0027]

[Outside 8]

[0028]

[Outside 9]

Next, synthetic examples of the above compounds will be shown.

(Synthesis Method of Exemplified Compound No. (11))
5.0 g of 3,4-dimethyliodobenzene (21.6 m
mol), toluidine 0.96 g (9.0 mmol),
27.6 g (200 mmol) of anhydrous potassium carbonate and 2.0 g of copper powder were added to 50 ml of o-dichlorobenzene, and the mixture was heated and refluxed for 8 hours while stirring in a nitrogen stream. After cooling, suction filtration was performed, and o-dichlorobenzene was removed from the filtrate under reduced pressure. The residue was separated and purified with a silica gel column, and Exemplified Compound No. 22.4 g of (11) (yield 79
%) Was obtained. Exemplified compound No. thus obtained The infrared absorption spectrum (KBr tablet method) of (11) is shown in FIG.

(Synthesis Method of Exemplified Compound No. (25))
2,3,4-Trimethyliodobenzene 15.0 g (6
1.0 mmol), toluidine 2.6 g (24.4 mm)
ol), anhydrous potassium carbonate 18.0 g and copper powder 7.4 g
Was added to 10 ml of o-dichlorobenzene, and the mixture was heated and refluxed for 16 hours while stirring in a nitrogen stream.

After cooling, suction filtration is carried out, and the filtrate is decompressed under reduced pressure.
-Dichlorobenzene was removed. The residue was separated and purified by a silica gel column, and the target compound, Exemplified Compound No.
5.27 g (yield 62.9%) of (25) was obtained.

Other compounds are synthesized in the same manner.

The photoconductor of the present invention uses a combination of the above-mentioned charge-transporting substance of the triarylamine compound and a suitable charge-generating substance.

Examples of the constitution of the photosensitive layer include the following forms.

(A) A charge-generating layer containing a charge-generating substance and a charge-transporting layer containing a charge-transporting substance, which are laminated in this order from the support side.

(B) A layer in which a charge transport layer and a charge generation layer are laminated in this order from the support side.

(C) A material containing both a charge generating substance and a charge transporting substance.

(D) A layer in which a charge generating layer and a charge transporting layer containing a charge generating substance and a charge transporting substance are laminated in this order from the support side.

Since the triarylamine compound used in the present invention has a high hole-transporting ability, it can be used as a charge-transporting substance. When the form of the photosensitive layer is (a), it is preferably negatively charged, when it is (b), it is preferably positively charged, and when it is (c) or (d), it can be used either positively or negatively.

Of the constitutions of (a) to (d), particularly (a)
Is preferable.

Examples of the charge generating substance include azo pigments (eg, monoazo, bisazo, trisazo, etc.), phthalocyanine pigments (eg, metal phthalocyanine, nonmetal phthalocyanine), and indigo pigments (eg, indigo, etc.).
Thioindigo etc.), polycyclic quinone pigments (eg anthraquinone, pyrene quinone etc.), perylene pigments (eg perylene anhydride, perylene imide etc.), squalium pigments, pyrylium, thiopyrylium salts, triphenylmethane pigments etc. Can be mentioned. Further, an inorganic material such as selenium, selenium-tellurium, or amorphous silicon can also be used as the charge generating substance.

In the present invention, it is particularly preferable to use titanyl phthalocyanine having the following structure as a charge generating substance.

[0044]

[Outside 10]

In addition to triphenylamine used as the charge transporting material in the present invention, a known charge transporting material may be contained in the photosensitive layer.

When the photosensitive layer is a single layer, the thickness of the photosensitive layer is 5
˜100 μm is preferable, and further preferably 10 to 60 μm. The single photosensitive layer preferably contains 10 to 70% by weight, and more preferably 20 to 70% by weight of each of the charge generating substance and the charge transporting substance.

When the photosensitive layer has a laminated structure, the thickness of the charge generation layer is preferably 0.001 to 5 μm, more preferably 0.01 to 2 μm, and the thickness of the charge transport layer is 5 to 40 μm, further 10.
-30 μm is preferable. The charge generation layer preferably contains a charge generation substance in an amount of 20 to 100% by weight, and more preferably 50 to 100% by weight. The charge transport layer preferably contains 10 to 500 parts by weight of triphenylamine used in the present invention per 100 parts by weight of the binder resin.

In the electrophotographic photosensitive member of the present invention, the material used for the photosensitive layer is combined with vacuum deposition, sputtering, CVD or a suitable binder resin, and the dip coating method, spray coating method, spinner coating method, roller coating method is used. It can be obtained by forming a film on a support using a coating method such as a Meyer bar coating method or a blade coating method.

The binder resin used in the photosensitive layer (in the case of a laminated structure, the charge generation layer and the charge transport layer) can be selected from a wide range of binder resins, for example, polycarbonate resin, polyester resin, polyarylate resin, Butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin, phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin, Examples of the vinyl chloride-vinyl acetate copolymer resin,
It is not limited to these. You may use these individually or in mixture of 2 or more types as a homopolymer or a copolymer polymer. Furthermore, polyvinylcarbazole and polyvinylanthracene can be used as the binder resin for the charge transport layer.

The support may be made of a metal or alloy such as aluminum, aluminum alloy, copper, titanium or stainless steel, or a polymer material such as polyethylene terephthalate, polybutylene terephthalate, phenol resin, polypropylene or polystyrene, or hard paper. It can be manufactured using the material. The shape of the support is preferably cylindrical, belt-shaped or sheet-shaped. When the material constituting the support has a high volume resistance, it is necessary to conduct a conductive treatment. The conductive treatment can be performed by forming a conductive thin film on the support or by dispersing a conductive substance in the support.

In the electrophotographic photoreceptor of the present invention, a protective layer may be provided on the photoconductive layer. The protective layer is mainly composed of resin. Examples of the material forming the protective layer include polyester, polyurethane, polyarylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, nylon, phenolic resin, acrylic resin, Examples thereof include silicone resin, epoxy resin, urea resin, allyl resin, alkyd resin, butyral resin and the like. The thickness of the protective layer is 0.05 to 15 μm, and further 1 to
10 μm is preferable.

An undercoat layer may be provided between the support and the photosensitive layer. The undercoat layer functions as a charge injection control at the interface and as an adhesive layer. The undercoat layer is mainly composed of a binder resin, but may contain a conductive material, a surfactant and the like. As the binder resin forming the undercoat layer, polyester, polyurethane, polyarylate, polyethylene, polystyrene,
Polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, polyamideimide, polysulfone, polyallyl ether, polyacetal, nylon, phenol resin, acrylic resin, silicone resin,
Examples thereof include epoxy resin, urea resin, allyl resin, alkyd resin, butyral resin and the like. The thickness of the undercoat layer is preferably 0.05 to 7 μm, more preferably 0.1 to 2 μm.

If desired, a sensitizer, an antioxidant, an ultraviolet absorber or a plasticizer may be added to the photosensitive layer.

Next, an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention will be described.

In FIG. 2, reference numeral 1 denotes a drum type photosensitive member of the present invention, which is rotationally driven around a shaft 1a in a direction of an arrow at a predetermined peripheral speed. In the course of its rotation, the photoconductor 1 is uniformly charged with a predetermined positive or negative potential on its peripheral surface by the charging means 2.
Next, the exposure unit 3 receives an optical image exposure L (slit exposure, laser beam scanning exposure, etc.) by image exposure means (not shown). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then toner-developed by the developing means 4 and the toner developed image is transferred by the transfer means 5 between the photosensitive member 1 and the transfer means 5 from a paper feeding portion (not shown) in synchronization with the rotation of the photosensitive member 1. The images are sequentially transferred onto the surface of the recording material P that has been taken out and fed.

The recording 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 image fixing and printed out as a copy.

After the image transfer, the surface of the photoreceptor 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
Also, transfer means are generally 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, at least one of the charging unit, the developing unit, and the cleaning unit may be integrated with the photosensitive member into one device unit, and the device unit may be detachable by using a guide unit such as a rail.

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 a document, or the document is read and converted into a signal, and the laser beam is scanned based on this signal. Or driving an LED array or a liquid crystal shutter array.

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

[0062]

EXAMPLES The present invention will be described below with reference to examples.

Example (1) 3 g of a bisazo pigment represented by the following structural formula was dissolved in a solution of 3 g of butyral resin (butyralization degree: 72 mol%) in 80 ml of cyclohexanone in a sand mill.
It was dispersed for a period of time to prepare a coating liquid.

[0064]

[Outside 11]

This coating solution was applied onto an aluminum sheet having a thickness of 50 μm by a Meyer bar so that the film thickness after drying would be 0.21 μm to form a charge generation layer.

Next, as the charge transporting substance, the above exemplified compound No. 10 g of (1) triphenylamine and 9 g of polycarbonate Z-type resin (weight average molecular weight 35,000) were dissolved in 65 g of monochlorobenzene, and this solution was applied onto the above charge generation layer with a Meyer bar to form a dry film. Thickness is 21
An electrophotographic photosensitive member of the present invention was prepared by using a charge transporting layer having a thickness of μm.

The electrophotographic photosensitive member thus prepared was used as an electrostatic copying paper tester Model-SP manufactured by Kawaguchi Electric Co., Ltd.
The electrostatic properties were examined by corona-charging at −5 KV by static method using −428, holding for 1 second in a dark place, and then exposing with white light with an illuminance of 20 Lux.

The charging characteristic is the surface potential (V
₀ ) Potential (V ₁ ) and potential (V
_The exposure amount (E _1/5 ) required to attenuate ₁ ) to 1/5 was measured and evaluated.

Further, in order to measure the fluctuations in the light potential and the dark potential when this photoconductor was repeatedly used, the photoconductor prepared in this example was attached to a drum, and this drum was manufactured by Canon Inc. It is mounted on a PPC copier NP-3825 to continuously copy 3000 sheets of recording paper, and the variation ΔV _L of the light potential ( _VL ) at the initial stage and after 3000 sheets are copied.
Also, the variation ΔV _D of the dark area potential (V _D ) was measured. The initial V _D and V _L are -700 V and-, respectively.
It was set to be 200V.

The surface of the electrophotographic photosensitive member prepared as described above was touched with a finger, and then the photosensitive member was left to stand at room temperature and normal pressure for 8 hours. In this way, it was observed whether the photosensitive layer had cracks.

Further, the surface of the electrophotographic photosensitive member prepared as described above is touched with a finger, and then this photosensitive member is moved to 75
It was placed in a constant temperature bath at ℃ for 1 week. Thus, it was observed whether or not crystallization of the charge transport material occurred.

The evaluation results are shown in Table 1.

Examples 2 to 8 and Comparative Examples 1 to 3 The charge transport material No. 1 used in Example 1 was used. Instead of (1), the triphenylamine exemplified above as shown in Table 1 was used as the charge transport material in Examples 2 to 8,
In Comparative Examples 1 to 3, the compounds shown below were used, and other electrophotographic photoreceptors were prepared in the same manner as in Example 1.

For each of the photoreceptors thus obtained, Example 1
It evaluated similarly to. The evaluation results are shown in Table 1.

[0075]

[Outside 12]

[0076]

[Table 1]

Example 9 N-methoxymethylated 6 nylon resin (weight average molecular weight 30,000) was prepared on an aluminum sheet having a thickness of 50 μm.
A solution prepared by dissolving 7 g and 11 g of alcohol-soluble copolymerized nylon resin (weight average molecular weight 30,000) in 90 g of methanol was applied with a Meyer bar, and the film thickness after drying was 1 μm.
An undercoat layer was provided.

Next, 4.3 g of the charge generating substance represented by the following structural formula was added to a liquid prepared by dissolving 3.9 g of phenoxy resin in 160 g of cyclohexanone, and dispersed for 21 hours by a ball mill. The dispersion is applied onto the previously formed undercoat layer by a blade coating method to give a film thickness of 0.2 after drying.
A charge generation layer of μm was formed.

[0079]

[Outside 13]

Next, as the charge transporting substance, the above exemplified compound No. (4) 9 g of triphenylamine and 10 g of polycarbonate Z-type resin (weight average molecular weight of 35,000) were dissolved in 69 g of monochlorobenzene, and this solution was applied onto the previously formed charge generation layer by a blade coating method. A charge transport layer having a thickness of 22 μm after drying was formed.

The electrophotographic photosensitive member thus prepared was used as an electrostatic copying paper tester Model-SP manufactured by Kawaguchi Electric Co., Ltd.
-428, statically corona-charged at -5KV, held in the dark for 1 second, and then exposed using a gallium / aluminum / arsenic ternary semiconductor laser (output 5mW, oscillation wavelength 780nm). I checked.

The charging characteristic is the surface potential (V
₀ ) Potential (V ₁ ) and potential (V
_The exposure amount (E _1/6 ) required to attenuate ₁ ) to 1/6 was evaluated.

Next, the photoconductor obtained as described above was attached to a drum, and this drum was attached to a laser beam printer (LBP-SX manufactured by Canon) which is an electrophotographic printer of the reversal development system, and the transfer current was turned off. the primary charging voltage when V _d1, the primary charging voltage at the time of transfer current ON as V _d2, measured so-called transfer memory (V _d1 -V _d2),
After that, an image forming test was conducted. The image forming conditions are as follows.

Surface potential after primary charging: -700V Surface potential after image exposure: -150V (exposure amount 1.0 μJ /
cm ² ) Transfer potential: +700 V Development polarity: Negative process speed: 47 mm / sec Development condition (development bias): -450 V Scanning method after image exposure: Image scan Pre-exposure before primary exposure: 8.0 Lux · sec full exposure image The formation was performed by line scanning with a laser beam in accordance with a character signal and a graphic signal, and good prints were obtained for both the character and the graphic.

Further, of the photoconductor prepared in the same manner as described above,
Evaluation of cracks in the charge transport layer and crystallization of the charge transport material was performed by the same method as in Example 1. The evaluation results are shown in Table 2.

Examples 10 to 14 Triphenylamine No. 1 used in Example 9 was used. An electrophotographic photosensitive member was prepared in the same manner as in Example 9 except that the triphenylamine exemplified above as shown in Table 2 was used as the charge transporting material instead of (4).

For each of the photoreceptors thus obtained, Example 9
It evaluated similarly to. The evaluation results are shown in Table 2.

Comparative Examples 4 to 6 Triphenylamine No. 1 used in Example 9 was used. An electrophotographic photosensitive member was prepared in the same manner as in Example 9 except that the compound represented by the following structural formula was used instead of (4).

The photoreceptors thus obtained were evaluated in the same manner as in Example 9. The evaluation results are shown in Table 2.

[0090]

[Outside 14]

[0091]

[Table 2]

Examples 15 to 20 The compounds represented by the following structural formulas were used as the charge generating substance, the triphenylamine exemplified above as shown in Table 3 was used as the charge transporting substance, and the others were the same as in Example 9. A photoconductor was prepared in exactly the same manner.

For each of the photoreceptors thus obtained, Example 9
It evaluated similarly to. The evaluation results are shown in Table 3.

[0094]

[Outside 15]

[0095]

[Table 3]

Example 21 4.4 g of 4- (4-dimethylaminophenol) -2,6-diphenylthiapyrylium burcreto and the above-exemplified compound No. 1 as a charge transport material. 5 g of triphenylamine of (2) was mixed with 100 g of a toluene (50 parts by weight) -dioxane (50 parts by weight) solution of 8 g of a copolyester resin (weight average molecular weight of 46,000), and dispersed by a ball mill for 20 hours. This dispersion was applied onto an aluminum sheet having a thickness of 50 μm with a Meyer bar and dried at 120 ° C. for 1 hour to form a photosensitive layer having a thickness of 11 μm. The initial characteristics of the thus prepared photoconductor were measured by the same method as in Example 1. The measurement results are shown below.

V ₀ = -700 V V ₁ = -685 (V) E _1/5 = 4.1 (Luxsec) Further, when cracking and crystallization of the photosensitive layer were evaluated in the same manner as in Example 1, No crack was observed even after 8 hours, and no crystallization was observed even after 1 week.

Example 22 A 30% methanol solution of alcohol-soluble nylon (6-66-610-12 quaternary nylon copolymer) was applied onto an aluminum sheet having a thickness of 50 μm, and the film thickness after drying was 1.9 μm. An undercoat layer was formed.

Next, the exemplified compound N is used as a charge-transporting substance.
o. (3) triphenylamine 9g and bisphenol A type polycarbonate resin (weight average molecular weight 28,000)
0) 10 g was dissolved in monochlorobenzene (60 parts by weight) -dichloromethane (20 parts by weight) solution 75 g, and this solution was applied on the undercoat layer prepared above by a Meyer bar,
A charge transport layer having a film thickness after drying of 20 μm was prepared.

Further, 4 g of the pigment represented by the following structural formula and 2.0 g of butyral resin (butyralization degree: 63 mol%) are dispersed in 65 ml of tetrahydrofuran by a sand mill, and the dispersion is dried on the charge transport layer prepared above. Was applied with a Meyer bar so that the film thickness was 1.0 μm to form a charge generation layer.

[0101]

[Outside 16]

The initial characteristics of the thus obtained photoreceptor are shown in Example 1.
It measured similarly to. However, the charging was positive. The measurement results are shown below.

V ₀ = + 710 (V) V ₁ = + 701 (V) E _1/5 = 2.4 (Lux · sec)

Example 23 On a plate-shaped glass support, 5 g of N-methoxymethylated 6 nylon resin (weight average molecular weight 28,000) and alcohol-soluble copolymerized nylon resin (weight average molecular weight 28,
000) 9 g with methanol 35 g and butanol 6
A solution dissolved in 5 g of the mixed solution was applied by dip coating, and an undercoat layer having a film thickness after drying of 1 μm was provided.

Next, the exemplified compound No. Monophenylbenzene (40 parts by weight) -dichloromethane (60 parts) was added to 10 g of triphenylamine (5) and 12 g of bisphenol A type polycarbonate resin (weight average molecular weight 27,000).
(Part by weight) dissolved in 100 g of the solution, and this solution is applied on the undercoat layer prepared above with a Meyer bar, and the film thickness after drying is 1
A 7 μm charge transport layer was prepared.

Next, an acrylic monomer 60 having the following structural formula
g, tin oxide ultrafine particles with an average particle size of 400Å before dispersion 4
0 g, 3 g of 2-methylthioxanthone as a photoinitiator,
280 g of methyl cellosolve was dispersed with a sand mill for 72 hours.

[0107]

[Outside 17]

Using this dispersion, a film was formed on the above charge transport layer by a beam coating method, and after the film was dried, it was photocured with a high pressure mercury lamp at a light intensity of 8 mW / cm ² for 30 seconds to obtain a thickness. A 2.1 μm protective layer was provided.

The charge transport layer of the sample thus obtained was observed with a transmission microscope (10 × magnification). The observation with the transmission microscope was performed while shining light from the glass support side at an angle of 15 ° to the glass support. As a result, neither cracks nor crystallization of the charge transport material occurred in the charge transport layer.

Although the sample prepared in this example is not a photoreceptor, the effect of the protective layer of the charge transport layer can be observed.

Example 24 3.2 g of a bisazo pigment represented by the following structural formula was dispersed in a sand mill for 24 hours together with a solution of 3 g of butyral resin (butyralization degree: 72 mol%) dissolved in 80 ml of cyclohexanone to prepare a coating solution. .

[0112]

[Outside 18]

This coating solution was applied on an aluminum sheet having a thickness of 50 μm by a Meyer bar so that the film thickness after drying would be 0.21 μm to form a charge generation layer.

Next, as a charge transport material, the above-mentioned exemplified compound No. (24) Triphenylamine 10 g and polycarbonate Z type resin (weight average molecular weight 20,000) 10
g was dissolved in 68 g of monochlorobenzene, and this solution was applied onto the above charge generation layer with a Meyer bar to form a charge transport layer having a dry film thickness of 25 μm, and the electrophotographic photoreceptor of the present invention was prepared.

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

Examples 25 to 32 The charge transport material Nos. Used in Example 24 were used. An electrophotographic photosensitive member was prepared in the same manner as in Example 24 except that the triphenylamine exemplified above as shown in Table 4 was used instead of (24).

For each of the photoreceptors thus obtained, Example 1
It evaluated similarly to. The evaluation results are shown in Table 4.

Comparative Example 7 The charge transport material No. 1 used in Example 24 was used. An electrophotographic photosensitive member was prepared in the same manner as in Example 24 except that the following compound was used instead of (24).

The photoreceptor thus obtained was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 4.

[0120]

[Outside 19]

[0121]

[Table 4]

Example 33 N-methoxymethylated 6 nylon resin (weight average molecular weight 30,000) was prepared on an aluminum sheet having a thickness of 50 μm.
A solution obtained by dissolving 0 g and 10.0 g of an alcohol-soluble copolymerized nylon resin (weight average molecular weight of 30,000) in 92 g of methanol was applied with a Meyer bar, and the film thickness after drying was 1
An undercoat layer of μm was provided.

Next, 3.2 g of the charge generating substance represented by the following structural formula was added to a solution prepared by dissolving 3.0 g of phenoxy resin in 160 g of cyclohexanone and dispersed by a ball mill for 24 hours. The dispersion is applied onto the previously formed undercoat layer by a blade coating method to give a film thickness of 0.2 after drying.
A charge generation layer of μm was formed.

[0124]

[Outside 20]

Next, as the charge transporting substance, the above-exemplified compound No. (27) Triphenylamine 9.5 g and polycarbonate Z type resin (weight average molecular weight 40,000) 1
0 g was dissolved in 68 g of monochlorobenzene, and this solution was applied onto the previously formed charge generation layer by a blade coating method to form a charge transport layer having a thickness of 25 μm after drying.

With respect to the photoreceptor thus obtained, the charging characteristics, the charge transport layer and the crystallization of the charge transport material were evaluated in the same manner as in Example 9. The evaluation results are shown in Table 5.

Further, when an image was formed by using a laser beam printer in the same manner as in Example 9 using the above-mentioned photoconductor, good prints were obtained for both characters and figures.

Examples 34 to 38 Triphenylamine No. 1 used in Example 33 was used. (27)
In place of the above, the triphenylamine exemplified above as shown in Table 5 was used as the charge transport material, and the others were used in Example 3
An electrophotographic photosensitive member was prepared in the same manner as in 3.

About each photoreceptor thus obtained, Example 3
It evaluated similarly to 3. The evaluation results are shown in Table 5.

Comparative Example 8 The triphenylamine No. used in Example 33 was used. (27)
An electrophotographic photosensitive member was prepared in the same manner as in Example 33 except that the compound represented by the following structural formula was used in place of

The photoreceptor thus obtained was evaluated in the same manner as in Example 33. The evaluation results are shown in Table 5.

[0132]

[Outside 21]

[0133]

[Table 5]

Examples 39 to 44 The compounds represented by the following structural formulas were used as the charge-generating substance, and the above-exemplified grated phenylamine as shown in Table 16 was used as the charge-transporting substance.
A photoconductor was prepared by the same method as described above.

About each of the photoreceptors thus obtained, Example 3
It evaluated similarly to 3. The evaluation results are shown in Table 6.

[0136]

[Outside 22]

[0137]

[Table 6]

Example 45 4.4 g of 4- (4-dimethylaminophenol) -2,6-diphenylthiapyrylium bercoolet and the above-exemplified compound No. 1 as a charge transport material. 5 g of triphenylamine of (2) was mixed with 80 g of a toluene (50 parts by weight) -dioxane (50 parts by weight) solution of 8 g of a copolyester resin (weight average molecular weight 40,000), and dispersed by a ball mill for 24 hours. This dispersion was applied onto an aluminum sheet having a thickness of 50 μm with a Meyer bar and dried at 120 ° C. for 1 hour to form a photosensitive layer having a thickness of 10 μm. The initial characteristics of the thus prepared photoconductor were measured by the same method as in Example 1. The measurement results are shown below.

V ₀ = −695 (V) V ₁ = −683 (V) E _1/5 = 4.4 Lux · sec) Further, cracks and crystallization of the photosensitive layer were evaluated in the same manner as in Example 1. No cracks were observed even after 8 hours, and no crystallization was observed even after 1 week.

Example 46 Alcohol-soluble nylon (6-66-610-12 quaternary nylon copolymer) was formed on an aluminum sheet having a thickness of 50 μm.
Of 30% methanol solution, and the film thickness after drying is 1.
An undercoat layer of 2 μm was formed.

Next, as the charge transport material, the above-exemplified compound No. 36 triphenylamine 9.5 g and bisphenol A type polycarbonate resin (weight average molecular weight 20,
000) 10 g with monochlorobenzene (60 parts by weight)
-Dissolved in 75 g of dichloromethane (20 parts by weight) solution,
This solution was applied on the undercoat layer prepared above with a Meyer bar to form a charge transport layer having a film thickness after drying of 18 μm.

Further, 3.2 g of the pigment represented by the following structural formula and 2.0 of a Brylal resin (degree of butyralization: 63 mol%): 2.0
g was dispersed in 70 ml of tetrahydrofuran with a sand mill, and this dispersion was applied onto the charge transport layer prepared above with a Meyer bar so that the film thickness after drying would be 0.8 μm to form a charge generation layer.

[0143]

[Outside 23]

The initial characteristics of the thus obtained photoreceptor are shown in Example 1.
It measured similarly to. However, the charging was positive. The measurement results are shown below.

V ₀ = + 700 (V) V ₁ = + 692 (V) E _1/5 = 3.1 (Lux · sec)

Example 47 A sample was prepared in the same manner as in Example 23 except that the charge transport layer was changed to the following.

The charge transport layer is formed of the above-mentioned compound No. 39 triphenylamine 10g and bisphenol A type polycarbonate resin (weight average molecular weight 20,000) 12g
Was dissolved in 100 g of a monochlorobenzene (40 parts by weight) -dichloromethane (60 parts by weight) solution, and this solution was formed on the previously prepared undercoat layer so that the thickness after drying was 20 μm.

The charge transport layer of the sample thus obtained was observed with a transmission microscope in the same manner as in Example 23. As a result, neither cracks nor crystallization of the charge transport material occurred in the charge transport layer.

[0149]

INDUSTRIAL APPLICABILITY In the electrophotographic photosensitive member of the present invention, cracks are not generated in the charge transport layer, and the charge transport material is not crystallized to cause phase separation. Further, the electrophotographic photosensitive member of the present invention has good sensitivity, stable electrophotographic characteristics even after repeated use, and is less likely to cause transfer memory in the reversal development method. Therefore, according to the present invention, a defect-free image can be obtained, and the quality of the image is less likely to deteriorate even if the image formation is repeated.

[Brief description of drawings]

FIG. 1 is a graph showing an infrared absorption spectrum (KBr tablet method) of an example of triphenylamine used in the present invention.

FIG. 2 is a side view showing an example of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging means 3 Exposure part 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Norihiro Kikuchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (8)

[Claims] 1. A phenyl group having a support and a photosensitive layer formed on the support, the phenyl group having two alkyl groups, wherein one of the alkyl groups is in the meta position with respect to the nitrogen atom. An electrophotographic photosensitive member comprising the photosensitive layer containing triphenylamine having at least two groups bonded to the photosensitive layer. 2. A triphenylamine having a support and a photosensitive layer formed on the support, the triphenylamine having at least two phenyl groups having three alkyl groups is contained in the photosensitive layer. And an electrophotographic photoreceptor. 3. The alkyl group of the three alkyl groups, wherein one alkyl group is in the meta position with respect to the nitrogen atom.
The electrophotographic photosensitive member described. 4. The electrophotographic photosensitive member according to claim 1, wherein one alkyl group is in a position para to the nitrogen atom. 5. The electrophotographic photosensitive member according to claim 1, wherein the alkyl group has 1 to 4 carbon atoms. 6. The electrophotographic photosensitive member according to claim 1, wherein titanyl phthalocyanine having the following structure is contained in the photosensitive layer as a charge generating substance. [Outer 1] 7. The electrophotographic photosensitive member according to claim 1 or 2, a charging unit for charging the electrophotographic photosensitive member, and an electrostatic latent image is formed by performing image exposure on the charged electrophotographic photosensitive member. An electrophotographic apparatus comprising: an image exposing unit for forming the image; and a developing unit for developing the electrophotographic photosensitive member on which the electrostatic latent image is formed with toner. 8. An electrophotographic apparatus comprising at least one of a charging means, a developing means and a cleaning means integrated with a photoconductor.