JPH0756366A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide an electrophotographic photoreceptor using an electric charge transferring material having electron transferring ability and a laminate type electrophotographic photoreceptor for positive electrification having excel lent electrophotographic performance. CONSTITUTION:A compd. having specified substituents and a structure represented by the general formula, etc., is incorporated into a photoreceptor. In the formula, Y is CN or halogen, m>=3, in the case of m=3, three Y's are identical with each other, in the case of m>=4, plural Y's may be different from each other, X is R1, COR1, COOR1, SOR1, SO2R1, CONHR1, CR2=CR2-R1, SO2NHR1, OR or phenyl which may have a substituent, n>=0, R1 is alkyl or phenyl which may have a substituent and R2 is H or R1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photosensitive member for forming an electrostatic latent image. More specifically, it relates to an electrophotographic photoreceptor having a layer containing a compound having an electron transporting ability.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic photosensitive member, one having a photosensitive layer containing an inorganic photoconductor such as selenium, zinc oxide, cadmium sulfide or silicon as a main component has been widely known. However, these are not always satisfactory in terms of properties such as thermal stability and durability, and have problems in manufacturing and handling.

On the other hand, a photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is relatively easy to manufacture, inexpensive, easy to handle, and generally a selenium photoreceptor. It has many advantages such as superior thermal stability. As such an organic photoconductive compound, poly-N-vinylcarbazole is best known, and a charge transfer complex formed from this and a Lewis acid such as 2,4,7-trinitro-9-fluorenone is used. Photoconductors having a photosensitive layer as a main component have already been put into practical use.

On the other hand, there is known a photoreceptor having a laminated type or single layer type function-separated type photosensitive layer in which a carrier generating function and a carrier transporting function of the photoconductor are shared by separate substances. Photoreceptors having a photosensitive layer composed of a carrier generation layer composed of a thin amorphous selenium layer and a carrier transport layer containing poly-N-vinylcarbazole as a main component have already been put into practical use.

However, poly-N-vinylcarbazole is
It lacks flexibility, its coating is hard and brittle, and it is prone to cracking and peeling. A photoreceptor using this is inferior in durability, and if a plasticizer is added to improve this defect, the residual potential becomes large during the electrophotographic process, and the residual potential is accumulated due to repeated use, and fogging gradually occurs. It becomes large and damages the image quality of the copy.

Further, since low molecular weight organic photoconductive compounds generally do not have film forming ability, they are used in combination with an appropriate binder, and the physical properties or photosensitivity of the film are selected by selecting the kind and composition ratio of the binder. However, the types of organic photoconductive compounds having high compatibility with the binder are limited. Actually, there are few kinds of binders that can be used for the constitution of the photosensitive layer of the photoconductor, especially the electrophotographic photoconductor.

For example, 2,5 described in US Pat. No. 3,189,447
-Bis (p-diethylaminophenyl) -1,3,4-oxadiazole has low compatibility with a binder commonly used as a material of a photosensitive layer of an electrophotographic photoreceptor, such as polyester and polycarbonate, and has electrophotographic properties. When the photosensitive layer is formed by mixing the components in a ratio required for arranging, crystals of oxadiazole will be deposited at a temperature of 50 ° C or higher, and there is a drawback that electrophotographic properties such as charge retention and sensitivity are deteriorated. .

On the other hand, the diarylalkane derivative described in US Pat. No. 3,820,989 has few compatibility problems with the binder, but has a low stability to light and is repeatedly charged and exposed for repeated transfer electrophotography. When it is used in the photosensitive layer of the above-mentioned photoconductor, the sensitivity of the photosensitive layer gradually decreases.

US Pat. No. 3,274,000, Japanese Patent Publication No. 47-3642
No. 8 describes different types of phenothiazine derivatives, but they all had the drawbacks of low photosensitivity and low stability during repeated use.

The stilbene compounds described in JP-A-58-65440 and JP-A-58-190953 have relatively good charge retention and sensitivity, but are not satisfactory in durability against repeated use. Absent.

As described above, no carrier transport substance having practically satisfactory properties for producing an electrophotographic photoreceptor has been found yet.

Further, since all of these charge-transporting substances have a hole-transporting ability, most of the developing systems adopting a negative charge on the surface of the photoconductor are adopted. For this reason, the toner that was conventionally used in high-speed machines cannot be used,
Currently, there are few high-quality images. Further, when the surface of the photoconductor is negatively charged as described above, there is a problem that not only the ozone is generated due to the reaction with oxygen in the air at the time of charging to harm the environment but also the surface of the photoconductor is deteriorated.

On the other hand, a positive charging laminated photoreceptor having a charge transport layer on the lower side and a charge generation layer on the upper side has been developed by reversing the layer structure of the photosensitive layer of the laminated photoreceptor. Since the charging potential is low and the printing durability is poor, a protective layer is further provided on the charge generation layer. However, this is also not a sufficient solution.

[0014]

In order to solve the above problems, a photoconductor in which a charge transport material having an electron transporting property is used in a charge transport layer and the surface of the photoconductor is positively charged. Should be configured. 2,4,7-Trinitro-9-fluorenone is known as such an electron-transporting material, but its solubility is poor and it is not possible to obtain practical sensitivity by combining it with an existing charge-generating substance. It was In addition, 2, 4,
As a result of improved studies on 7-trinitro-9-fluorenone, in recent years, an electron transporting substance having a solubilizing group introduced into an electron acceptor structure has been proposed. For example, Japanese Patent Laid-Open No. 1-206349
No. 2-135362, No. 2-214866, No. 3-290666 and “Japan Hardcopy '92” Proceedings, 173, (1992). However, in the present situation, when any of the compounds is combined with an existing charge generating substance to form a photoreceptor, the sensitivity is still insufficient in practical use, and a good image cannot be obtained.

In view of the above problems, it is an object of the present invention to provide an electrophotographic photosensitive member using a charge transporting substance having an electron transporting ability.

Another object of the present invention is to provide a positive charging laminated electrophotographic photoreceptor having excellent electrophotographic performance, that is, high sensitivity, low residual potential and good image characteristics.

[0017]

[Means for Solving the Problems] As a result of intensive studies in accordance with the above-mentioned purpose, the following general formulas [1], [2], [3],
It has been found that an electrophotographic photoreceptor containing at least one of the compounds represented by [4] and [5] has excellent utility.

An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [1] as a charge transporting substance. .

[0019]

[Chemical 6]

[Wherein Y: CN or halogen, m ≧ 3
(Y is the same when m = 3, and may be different when m ≧ 4. X: R ₁ , COR ₁ , COOR ₁ , SOR ₁ ,
_{SO 2 R 1, CONHR 1,} CR 2 = CR 2 -R 1, SO 2 N
HR ₁ , OR ₁ , phenyl (substituents may be present) n
≧ 0, R ₁ : alkyl, phenyl (may have a substituent) R ₂ : H, or R ₁ ] In the general formula [1], Y is a CN group and X is COR ₁ , COO
It is any group of R ₁ .

An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [2] as a charge transporting substance. .

[0022]

[Chemical 7]

[Wherein m ≧ 1, X: CN, NO ₂ , halogen, R ₁ , COR ₁ , COOR ₁ , SOR ₁ , SO ₂ R ₁ ,
_{CONHR 1, CR 2 = CR 2} -R 1, SO 2 NHR 1, OR
₁ , or phenyl (may have a substituent) n ≧ 0,
R ₁ : alkyl, phenyl (may have a substituent)
R ₂ : H, or R ₁ ] In the general formula [2], a particularly desirable one is an electrophotographic photosensitive member characterized by m ≧ 3 and X being a group of either COR ₁ or COOR _1. is there.

An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [3] as a charge transporting substance. .

[0025]

[Chemical 8]

[Wherein Z ₁ : H, R ₁ , COR ₁ , COO
R ₁ , CR ₂ = CR ₂ -R ₁ , or phenyl (may have a substituent) Z ₂ : Z ₁ or CN, Y: CN, NO ₂ , C
F ₃ , or halogen, m ≧ 1, X: R ₁ , COR ₁ , CO
OR ₁ , SOR ₁ , SO ₂ R ₁ , CONHR ₁ , CR ₂ = CR
_2- R ₁ , SO ₂ NHR ₁ , OR ₁ , or phenyl, n ≧
0, R ₁ : alkyl, or phenyl (may have a substituent) R ₂ : H, or R ₁ ] In the general formula [3], particularly desirable is m ≧ 3, Y is CN, or CF. ₃ , X
Is a group of either COR ₁ or COOR ₁ , which is an electrophotographic photosensitive member.

An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [4] as a charge transporting substance. .

[0028]

[Chemical 9]

[In the formula, Q: alkyl, phenyl, condensed polycycle, or heterocycle (any of which may have a substituent), Y: CN, NO ₂ , CF ₃ , or halogen, m ≧
1, X: R ₁ , COR ₁ , COOR ₁ , SOR ₁ , SO
₂ R ₁ , CONHR ₁ , CR ₂ = CR ₂ -R ₁ , SO ₂ NH
R ₁ , OR ₁ , or phenyl, n ≧ 0, R ₁ : alkyl,
Or phenyl (which may have a substituent) R ₂ : H, or R ₁ ] In the general formula [4], a particularly desirable one is
m ≧ 3, Y is CN, or CF ₃ , X is COR ₁ , COOR
An electrophotographic photosensitive member characterized by being a group of any one of ₁ .

An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [5] as a charge transporting substance. .

[0031]

[Chemical 10]

[Wherein Y: CN, NO ₂ , CF ₃ or halogen, m ≧ 1, X: R ₁ , COR ₁ , COOR ₁ , SO
_{R 1, SO 2 R 1,} CONHR 1, CR 2 = CR 2 -R 1, S
O ₂ NHR ₁ , OR ₁ , or phenyl, n ≧ 0, R ₁ : alkyl, or phenyl (both may have a substituent).
R ₂ : H, or R ₁ ] In the general formula [5], particularly desirable is m ≧ 2, Y is CN, or CF ₃ and X is CO.
An electrophotographic photoconductor characterized by being _one of R ₁ and COOR ₁ .

The high performance of the present invention as a charge transport material is
This seems to be because the long-term compatibility with the binder is kept stable as compared with the conventional charge transport material.

Next, the specific compounds represented by the general formulas [1] to [5] and the synthesis examples thereof will be sequentially described as follows.

(1) As those belonging to the general formula [1],

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

Exemplified Compound 1-19 according to the following synthetic route
Was synthesized.

[0041]

[Chemical 15]

Using perfluorobenzoic acid (manufactured by Aldrich) as a starting material, a known method (Can, J, Chem 4
6, 2549 (1968)), compound 3 was synthesized.

10 g of Compound 3 was placed in a 200 ml four-headed flask, 6.6 g of malononitrile (manufactured by Tokyo Kasei), 100 ml of methanol and 1 drop of piperidine were placed therein, and the mixture was heated under reflux for 24 hours. After cooling, the crystals were collected by filtration and washed well with methanol and water. After drying, the crystals were applied to a silica gel column.
The toluene: n-hexane = 1: 1 eluate was crystallized from ethyl acetate to give 7.6 g of orange crystals of Exemplified Compound 1-19 (yield).
65%). The melting point was 145-147 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound 1-19 was confirmed.

[0044] (2) As those belonging to the general formula [2],

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

Exemplified Compound 2-15 according to the following synthetic route
Was synthesized.

[0050]

[Chemical 20]

Using 3,5-bis (trifluoromethyl) benzoyl chloride (manufactured by Aldrich) as a starting material, a known method (Organic Synthesis Collective Volume) 1,9
9, (1941)), and compound 2 was synthesized.

10 g of compound 2 was placed in a 200 ml four-headed flask, and 5.1 g of malononitrile (manufactured by Tokyo Kasei) and methanol were added.
100 ml and 1 drop of piperidine were added and refluxed for 24 hours. After cooling, the crystals were collected by filtration and washed well with methanol and water.
After drying, the crystals were applied to a silica gel column. The toluene: n-hexane: 1: 1 eluate was crystallized with ethyl acetate to give 8.7 g of orange crystals of the exemplified compound 2-15 (yield 78
%) Was obtained. The melting point was 136-138 ° C as a result of measurement according to the Japanese Pharmacopoeia melting point measuring method.

Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound 2-15 was confirmed.

[0054] (3) As those belonging to the general formula [3],

[0055]

[Chemical 21]

[0056]

[Chemical formula 22]

[0057]

[Chemical formula 23]

[0058]

[Chemical formula 24]

Exemplified Compound 3-13 according to the following synthetic route
Was synthesized.

[0060]

[Chemical 25]

Using 3,5-bis (trifluoromethyl) benzoyl chloride (manufactured by Aldrich) as a starting material, a known method (Organic Synthesis Collective Volume 1, 9) was used.
9, (1941) and Bull Chem, Soc Jap, 44, 2285 (1971)).
According to the above, compound 3 was synthesized.

10 g of compound 3 was placed in a 300 ml four-headed flask, 0.4 g of octanal was added, 3.5 g of octanal (manufactured by Kanto Chemical Co., Inc.), 150 ml of ethanol and 0.4 g of piperidine were added, and the mixture was heated under reflux for 72 hours. After allowing to cool, the crystals were collected by filtration and washed with ethanol. After drying, the crystals were applied to a silica gel column. Toluene: n-hexane: 3: 1 eluate,
Recrystallized from toluene to give yellow crystals of Exemplified Compound 3-13
7.2 g (yield 55%) was obtained. The melting point was 161-162 ° C as a result of measurement according to the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, Exemplified Compound 3-13
The structure of was confirmed.

[0063] (4) As those belonging to the general formula [4],

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

Exemplified Compound 4-1 according to the following synthetic route
Was synthesized.

[0070]

[Chemical 31]

Exemplified Compound 4-1 was synthesized according to the above synthetic route. Using 3,5-bis (trifluoromethyl) benzoyl chloride (manufactured by Aldrich) as a starting material, a known method (Organic Synthesis Collective Volume 1, 99, (19
Compound 2 was synthesized according to (41)).

10 g of compound 2 was placed in a 300 ml four-headed flask, 20 g of zinc chloride, 3.8 g of 2-ethylaniline (manufactured by Aldrich) and 100 ml of ODB (o-dichlorobenzene) were added, and an ester tube and a thermometer were attached to Ar. The mixture was heated under reflux for 59 hours under an air stream. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane: 1:
The 1-eluted portion was crystallized with n-hexane to give Exemplified Compound 4
-1 g of red powder (7.8 g, yield 61%) was obtained. The melting point was 173-174 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound 4-1 was confirmed.

[0073] (5) As those belonging to the general formula [5],

[0074]

[Chemical 32]

[0075]

[Chemical 33]

[0076]

[Chemical 34]

Exemplified Compound 5-1 was synthesized according to the following synthetic route.
Was synthesized.

[0078]

[Chemical 35]

Using 3,5-bis (trifluoromethyl) benzoyl chloride (manufactured by Aldrich) as a starting material, a known method (Organic Synthesis Collective Volume 1, 9
9, (1941)), and compound 2 was synthesized.

10 g of Compound 2 was placed in a 300 ml four-headed flask, 5.8 g of bis (trimethylsilyl) carbodiimide (manufactured by Tokyo Kasei), 150 ml of acetonitrile and 0.5 g of cesium fluoride (manufactured by Kanto Kasei) were added, and under Ar flow, It was stirred for 72 hours. For the post-treatment, the solid was collected by suction filtration, thoroughly washed with acetonitrile, and subjected to a silica gel column chromatogram. Toluene: n-hexane: 1: 1 eluate was crystallized from n-hexane to give a yellow powder of Exemplified Compound 5-1.
5.1 g (yield 48%) was obtained. The melting point was 161-163 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound 1 was confirmed.

[0081]

[0082]

In the electrophotographic photoreceptor of the present invention, examples of the conductive support include metal pipes, metal plates, metal sheets,
A metal foil, a polymer film subjected to a conductive treatment, a polymer film provided with a vapor-deposited layer of a metal such as aluminum, a metal oxide, a polymer film coated with a quaternary ammonium salt, or paper is used.

In the electrophotographic photosensitive member of the present invention, the photosensitive layer is provided on the conductive support, but the photosensitive layer may have a single layer structure, or a laminated structure in which the charge generating layer and the charge transporting layer are functionally separated. It may be one. An adhesive layer may be provided between the conductive support and the photosensitive layer.

As shown in FIG. 1A, the photoreceptor of the present invention comprises a conductive support 1 and a charge generation layer (CGL) 2 containing a charge generation material (CGM) as a main component and an n-type charge transport layer. Charge transport layer (CT) containing a substance (CTM) as a main component
L) 3 is provided with a photosensitive layer 4 formed of a laminate. The photosensitive layer 4 may be provided via an intermediate layer 5 provided on the conductive support 1, as shown in FIGS. Thus, when the photosensitive layer 4 has a two-layer structure, a photoreceptor having the most excellent electrophotographic characteristics can be obtained. Further, in the present invention, as shown in FIGS. 1 (e) and (f), a photosensitive layer 4 formed by dispersing fine CGM 7 in a layer 6 containing CTM as a main component is provided on a conductive support 1. Directly or in the middle layer 5
You may provide through.

Further, a protective layer 8 (OCL) may be provided on the photosensitive layer 4 if necessary.

CGM may be added to the n-type CTL in the above structure, or n-type CTM may be added to the CGL.

Further, a protective layer (OCL) may be provided on the photosensitive layer 4 if necessary.

N-type CTM or p-type CTM may be added to this OCL.

A p-type CTM may be used in combination with the photoreceptor using the n-type CTM of the present invention.

In the case where p-type CTM is used in combination, the most preferable embodiment is a structure in which a layer made of n-type CTM is provided as the uppermost layer and a p-type CTM layer is provided on the support side.

Concretely, as the layer constitution, (g) to (g) of FIG.
A layer structure such as (j) is preferable.

CGL which constitutes the photosensitive layer 4 having a two-layer structure
2. The CTL 3 may be formed by the following method depending on the characteristics of CTM and CGM, directly or on the conductive support 1 which is the lower layer surface, or when an intermediate layer such as an adhesive layer or a barrier layer is provided if necessary. it can.

(1) Vapor deposition method (2) Coating method a) Method of applying a solution coating in which CGM and CTM are dissolved in a suitable solvent b) CGM and CTM are finely dispersed in a dispersion medium by a ball mill, homomixer or the like. A method of applying a dispersion coating material obtained by mixing and dispersing it into particles and, if necessary, a binder.

Examples of the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a CVD method and the like, and a coating method includes a dipping method, a spray method, an air doctor method, a doctor blade method and a reverse method. An appropriate method is selected according to the physical properties of the coating material such as the roll method.

The adhesive layer is formed of a resin alone, is applied with a low resistance compound such as tin oxide, indium oxide or titanium oxide dispersed in a resin, or is applied with aluminum oxide, zinc oxide, silicon oxide or the like. The vapor deposition film of
The resin used for the adhesive layer is not particularly limited, and examples thereof include vinylidene chloride-vinyl chloride copolymer, water-soluble polyvinyl butyral resin, alcohol-soluble polyamide resin, vinyl acetate-based resin, polyvinyl alcohol, nitrocellulose, and polyimide resin. To be

The thickness of the binder layer is preferably about 0.01 to 10 μm, and particularly preferably 0.01 to 1 μm.

When the photosensitive layer is a single layer, the compound represented by the above general formulas [1] to [5] is contained as a sensitizer in the photosensitive layer composed of a known material such as polyvinylcarbazole. And those containing a compound represented by the above general formula [1] to [5] as an electron transporting substance in a photosensitive layer containing a known charge generating substance. On the other hand, when the photosensitive layer is a laminated type, the charge generation layer may be one obtained by vapor deposition of a charge generation substance on a conductive support, and a coating containing a charge generation substance and a binder resin as main components. It may be formed by applying a liquid.

Any known charge generating substance and binder resin can be used.

For example, as the charge generating substance, an inorganic semiconductor such as selenium type, an organic semiconductor such as polyvinylcarbazole, a bisazo type compound, a trisazo type compound, a metal-free phthalocyanine type compound, a metal phthalocyanine type compound,
Organic pigments such as pyrylium compounds, squarylium compounds, cyanine compounds, perylene compounds and polycyclic quinone compounds can be used. Among them, preferable charge generating substances include, for example, Y-type titanyl phthalocyanine pigments having an X-ray diffraction peak at 27.2 ° in JP-A-64-17066,
A having an X-ray diffraction peak at 26.3 ° in JP-A-62-67094
Type titanyl phthalocyanine pigment, B type titanyl phthalocyanine pigment having an X-ray diffraction peak at 28.7 ° of JP-A-61-239248, metal-free phthalocyanine pigment of JP-B-49-4338, and copper phthalocyanine of JP-A-57-163239. Pigments, vanadyl phthalocyanine pigments of JP-A-57-148747, perylene pigments of JP-A-49-128734, condensed polycyclic pigments of JP-A-47-18544, and bisazo pigments of JP-A-1-150145. is there. As the binder resin, polystyrene, silicone resin, polycarbonate resin, acrylic resin, methacrylic resin, polyester, vinyl polymer, cellulose resin, butyral resin, silicone modified butyral resin, alkyd resin and the like can be used.

The thickness of the charge generation layer is preferably about 0.01 to 10 μm, particularly preferably 0.05 to 2 μm.

A charge transport layer is formed on the charge generation layer. The charge transport layer is composed of the compounds represented by the above general formulas [1] to [5] and a binder resin,
A coating solution containing the compounds represented by the above general formulas [1] to [5], a binder resin, and a suitable solvent as a main component is coated on the charge generation layer with an applicator, a bar coater, a dip coater, or the like. Formed by. In this case, the mixing ratio of various compounds and the binder resin is preferably 1: 100 to 100: 1, and particularly preferably 1:20 to 20: 1.

As the binder resin used in the charge transport layer, any known binder resin can be used. For example, as the binder resin, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, vinyltoluene-styrene copolymer, styrene-modified alkyd resin, silicone-modified alkyd resin, soybean oil-modified alkyd resin, vinylidene chloride-vinyl chloride Resin, polyvinyl butyral, nitrated polystyrene, polymethylstyrene,
Polyisoprene, polyester, phenol resin, ketone resin, polyamide, polycarbonate, polythiocarbonate, polyacrylate, polyhaloacrylate,
Examples thereof include vinyl acetate resin, polystyrene, polyallyl ether, polyvinyl acrylate, polysulfone, polymethacrylate and the like. Among them, biphenyl Z type polycarbonate is particularly preferable. Further, an electron-donating substance may be added to the charge transport layer to produce a bipolar photoreceptor.

Further, an antioxidant or a radical trap agent may be added to the charge transport layer.

The thickness of the charge transport layer is preferably 2 to 100 μm, particularly preferably 5 to 50 μm.

In the electrophotographic photosensitive member of the present invention,
A barrier layer may be provided on the conductive support. The barrier layer is
It is effective in preventing the injection of unnecessary charges from the conductive support and has the effect of improving the image quality. Materials for forming the barrier layer include metal oxide such as aluminum oxide, acrylic resin, phenol resin, polyester resin, polyurethane and the like. The barrier layer may be provided on the adhesive layer or may be provided on the lower side.

[0106]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

The following examples are for each compound represented by the general formulas [1] to [5] according to the present invention.
[5] Groups are categorized, and each group has: (I) Sensitivity evaluation (Evaluation 1) ... Examples 1 to 10 and Comparative Example (1) (II) Durability evaluation (Evaluation 2) ... Example 11 ˜20, Comparative Example (2) (III) Image Quality Evaluation (Evaluation 3) ... Comprising Examples 21 to 30 and Comparative Example (3), except that each group is different in the compound according to the present invention.
The samples of Examples and Comparative Examples having exactly the same shape, the same kind, and the same size are assembled. The comparative examples of each group are the same for each evaluation.

(I) Sensitivity Evaluation Evaluation 1 The electrophotographic photosensitive member samples obtained in Example 1 and Comparative Example 1 were charged to +800 V by using an electrostatic copying paper test apparatus EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.). , 10 lux of white light was exposed, and the amount of exposure until the surface potential was halved was determined as the sensitivity. The results are shown in (I) of Tables 1 to 15.

Examples 1 to 10 A 0.5 μm-thick intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a PET film on which aluminum was vapor-deposited, and a perylene pigment (Chemical Formula 36) shown in Chemical formula 36 CGM-1) 1 part, polyvinyl butyral resin "ESREC BLS" (manufactured by Sekisui Chemical Co., Ltd.) 0.2 parts, and methyl ethyl ketone 50 parts as a dispersion medium are dispersed by using a sand mill to apply a solution using a wire bar to form a film having a thickness of 0.3 μm. The charge generation layer of was formed. Then, 1 part of the exemplified compound shown in each (I) of Tables 1 to 15 and the polycarbonate resin "Iupilon Z"
-200 "(manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 10 parts of tetrahydrofuran and (THF) and blade-coated on the charge generation layer to form a charge transport layer having a thickness of 20 μm.

Comparative Example 1 Comparative Compound 1 shown in “Chemical Formula 36” in place of Exemplified Compound 1-1
Comparative samples were prepared in the same manner as in Example 1 except that was used.

(II) Durability Evaluation Evaluation 2 The electrophotographic photoreceptor samples obtained in Example 11 and Comparative Example 2 were subjected to the following actual measurements with a U-BIX1017 remodeling machine manufactured by Konica Corporation at the initial stage and after copying 10,000 sheets. The value was evaluated. The results are shown in Tables 1 to 15 (II).

Vb: Surface potential for original with black area potential, reflection density of 1.3 Vw: Surface potential for original with white area potential, reflection density of 0.0 Vr: Residual potential, surface potential after neutralization Examples 11 to 20 Aluminum was vapor-deposited. A 0.5 μm-thick intermediate layer made of polyamide resin “X-1874M” (manufactured by Daicel Huls) was provided on a PET film, and a pigment X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals) (CGM-2) was provided on the intermediate layer. ) 1
Section, polyvinyl butyral resin "ESREC BX-1"
A solution in which 0.4 part (manufactured by Sekisui Chemical Co., Ltd.) and 50 parts of methyl isopropyl ketone as a dispersion medium were dispersed using a sand mill was applied using a wire bar to form a charge generation layer having a thickness of 0.3 μm. Then, the exemplified compounds 1 of each (II) in Tables 1 to 15
Parts and 1.5 parts of a polycarbonate resin "UPILON Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 10 parts of THF and blade-coated on the charge generation layer to form a charge transport layer having a thickness of 20 [mu] m.

Comparative Example 2 Comparative Compound 2 shown in “Chemical Formula 36” in place of Exemplified Compound 1-2
Comparative samples were prepared in the same manner as in Example 11 except that was used.

(III) Image Quality Evaluation Evaluation 3 With respect to the electrophotographic photoreceptor samples obtained in Example 21 and Comparative Example 3, digital copy “Ko” manufactured by Konica Corporation was used.
Images were output with a modified machine of "nica9028" (charge polarity: positive, reverse development). Next, these samples were left in a low temperature (10 ° C.) environment for 1 month, and thereafter, images were displayed again under the same conditions. The black spots on the white background portion of these copied images were evaluated. The results are shown in Tables 1 to 15 (III).

The evaluation of the black spots was performed by measuring the size and number of the black spots using an image analyzer "Omnicon 300 type" (manufactured by Shimadzu Corporation), and a black spot having a diameter of 0.05 mm or more was 1 cm ^2.
It was performed by judging how many there are. The criteria for evaluating the black spots are as shown below. It should be noted that if the result of the black spot determination is ⊚ or ◯, it is practical, but if it is Δ, it may not be practical, and if it is ×, it is not practical.

Number of black spots having a diameter of 0.05 mm or more (pieces / cm ² ) Black spot determination 0 ◎ 1-3 ○ 4-10 △ 11 or more × Examples 21-30 Polyamide resin “CM8000” on a cylindrical aluminum substrate. (Manufactured by Toray Industries, Inc.), an intermediate layer having a thickness of 0.5 μm is provided, and a Bragg angle 2θ in X-ray diffraction of 9.5 °, 24.1 °, 27.
Titanine phthalocyanine (CGM having a peak at 2 °
-3) 1 part, 0.5 part of silicone-butyral resin A liquid in which 50 parts of methyl isopropyl ketone as a dispersion medium was dispersed using a sand mill was dip-coated to form a charge generation layer having a thickness of 0.3 μm. Next, 1 part of the exemplified compound shown in each (III) of Tables 1 to 15 and the polycarbonate resin "Iupilon Z-
200 parts (manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 10 parts of THF and was blade-coated on the charge generation layer to form a charge transport layer having a film thickness of 20 μm.

Comparative Example 3 A comparative sample was prepared in the same manner as in Example 21 except that Comparative Compound 3 shown in "Chemical Formula 36" was used in place of Exemplified Compound 1-3.

[0118]

[Chemical 36]

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Table 3]

[0122]

[Table 4]

[0123]

[Table 5]

[0124]

[Table 6]

[0125]

[Table 7]

[0126]

[Table 8]

[0127]

[Table 9]

[0128]

[Table 10]

[0129]

[Table 11]

[0130]

[Table 12]

[0131]

[Table 13]

[0132]

[Table 14]

[0133]

[Table 15]

As is clear from the above-mentioned tables, the electrophotographic photosensitive member using the charge transporting material of the present invention has a sensitivity equal to or higher than that of the conventional charge photographic photosensitive member using the charge transporting material. Therefore, it can be seen that the photoreceptor characteristics are stable during repeated use, and that the occurrence of image defects is extremely small even after storage at low temperature.

[0135]

INDUSTRIAL APPLICABILITY The compound of the present invention has an electron transporting ability and is practical, that is, it can provide a positive charging photoreceptor having high sensitivity, low residual potential, and good image retention.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an exemplary embodiment of a photoconductor of the present invention.

FIG. 2 is a cross-sectional view of an exemplary embodiment of a photoconductor of the present invention.

[Explanation of symbols]

1 Conductive Support 2 Charge Generation Layer (CGL) 3 Charge Transport Layer (CTL) 4 Photosensitive Layer 5 Intermediate Layer 6 Layer Containing Charge Transport Material (CTM) 7 Charge Generation Material (CGM) 8 Protective Layer (OCL) 9 Charge transport layer (CTL) containing p-type charge transport material (p-type CTM) 10 Layer containing p-type charge transport material (p-type CTM) and charge generating material (CGM)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Motoko Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (10)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [1] as a charge transporting substance. Photoconductor. [Chemical 1] [Wherein Y: CN, or halogen, m ≧ 3 (Y is the same when m = 3, and may be different when m ≧ 4).
X: R ₁ , COR ₁ , COOR ₁ , SOR ₁ , SO ₂ R ₁ , C
ONHR ₁ , CR ₂ = CR ₂ -R ₁ , SO ₂ NHR ₁ , OR,
Phenyl (may have a substituent) n ≧ 0, R ₁ : alkyl, phenyl (may have a substituent) R ₂ :
H, or R ₁ ] 2. In the general formula [1], Y is a CN group and X is
Is a group of either COR ₁ or COOR ₁ , and the electrophotographic photosensitive member according to claim 1. 3. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [2] as a charge transporting substance. Photoconductor. [Chemical 2] [Wherein m ≧ 1, X: CN, NO ₂ , halogen, R ₁ , C
OR ₁ , COOR ₁ , SOR ₁ , SO ₂ R ₁ , CONHR ₁ ,
CR ₂ = CR ₂ -R ₁ , SO ₂ NHR ₁ , OR ₁ , or phenyl (which may have a substituent) n ≧ 0, R ₁ : alkyl, phenyl (which may have a substituent) R ₂ : H or R ₁ ] 4. In the general formula [2], m ≧ 3 and X are
The electrophotographic photosensitive member according to claim 3, wherein the electrophotographic photosensitive member is _one of COR ₁ and COOR ₁ . 5. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [3] as a charge transporting substance. Photoconductor. [Chemical 3] [Wherein Z ₁ : H, R ₁ , COR ₁ , COOR ₁ , CR ₂ =
CR ₂ -R _1, or phenyl (which may have a substituent.)
Z ₂ : Z ₁ or CN, Y: CN, NO ₂ , CF ₃ , or halogen, m ≧ 1, X: R ₁ , COR ₁ , COOR ₁ , SO
_{R 1, SO 2 R 1,} CONHR 1, CR 2 = CR 2 -R 1, S
O ₂ NHR ₁ , OR ₁ , or phenyl, n ≧ 0, R ₁ : alkyl, or phenyl (substituents may be present).
R ₂ : H, or R ₁ ] 6. In the general formula [3], m ≧ 3 and Y are C
6. The electrophotographic photosensitive member according to claim 5, wherein N, or CF ₃ , X is a group of either COR ₁ or COOR ₁ . 7. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [4] as a charge transporting substance. Photoconductor. [Chemical 4] [In the formula, Q: alkyl, phenyl, condensed polycycle, or heterocycle (any of which may have a substituent), Y: C
N, NO ₂ , CF ₃ , or halogen, m ≧ 1, X: R ₁ ,
COR ₁ , COOR ₁ , SOR ₁ , SO ₂ R ₁ , CONH
R ₁ , CR ₂ = CR ₂ -R ₁ , SO ₂ NHR ₁ , OR ₁ , or phenyl, n ≧ 0, R ₁ : alkyl, or phenyl (which may have a substituent) R ₂ : H, or R ₁ ] 8. In the general formula [4], m ≧ 3 and Y are C
8. The electrophotographic photosensitive member according to claim 7, wherein N, or CF ₃ , X is a group of either COR ₁ or COOR ₁ . 9. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [5] as a charge transporting substance. Photoconductor. [Chemical 5] [In the formula, Y: CN, NO ₂ , CF ₃ , or halogen, m ≧
1, X: R ₁ , COR ₁ , COOR ₁ , SOR ₁ , SO
₂ R ₁ , CONHR ₁ , CR ₂ = CR ₂ -R ₁ , SO ₂ NH
R ₁ , OR ₁ , or phenyl, n ≧ 0, R ₁ : alkyl,
Or phenyl (both may have a substituent) R ₂ :
H, or R ₁ ] 10. The electrophotography according to claim 9, wherein in general formula [5], m ≧ 2, Y is CN, or CF ₃ , X is a group of COR ₁ or COOR _1. Photoconductor.