JPH04330451A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a good image having high sensitivity and no image defect and no image inferiority such as white dot, black spot, fogging or lowering of density by containing specific bis-styryl compound. CONSTITUTION:Bis-styryl compound expressed by the formula I is contained. In the formula I, (n) is >=0 and when (n)=0, R<1> is chlorine atom, cyano group substituted at 2- or 3- positions or fluorine atom, bromine atom, iodine atom and a functional group selected from 1-4C alkyl haride substituted at 2-, 3- or 4- positions to substituted amino group and when (n) >=1, R<1> is halgen atom, cyano group or 1-4C alkyl haride substituted at 2-, 3- or 4- positions to substituted amino group. And R<2> is a functional group selected from 1-4C lower alkyl group, halogen atom, cyano group and two Cy are heterocyclic group or heterocyclic group condensated with benzene ring.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to the use of a carrier-generating substance and a key.
Electrophotographic material having a photosensitive layer containing a carrier transport substance
Bissus suitable as the carrier transport substance in the optical body
Regarding electrophotographic photoreceptors containing tyryl compounds.
be. [Prior Art] Conventionally, electrophotographic photoreceptors have been made of selenium,
Inorganic photoconductors such as zinc oxide, cadmium sulfide, silicon, etc.
Photoreceptors containing as a main component were widely known. death
However, these properties do not necessarily satisfy properties such as thermal stability and durability.
It is not something that can be added, and there are also problems in manufacturing and handling.
There was a problem. [0003] On the other hand, photoconductive compounds mainly composed of organic photoconductive compounds
A photoreceptor having a photosensitive layer is relatively easy to manufacture.
, low cost, easy handling, and one
It generally has better thermal stability than selenium photoreceptors. like this
Examples of the organic photoconductor compound include poly-N-vinyl carbon.
Rubazole is well known, and it and 2,4,7-t
formed from Lewis acids such as linitro-9-fluorenone.
A photoreceptor having a photosensitive layer containing a charge transfer complex as a main component
has already been put into practical use. On the other hand, the carrier generation function of the photoconductor
Assign the carrier transport function to separate substances.
Has a laminated type or single layer type functionally separated photosensitive layer.
Photoreceptors that do this are known. For example, amorphous selenium thin layer
A carrier generation layer consisting of poly-N-vinylcarbazo
and a carrier transport layer containing silica as a main component.
Photoreceptors having a light layer have already been put into practical use. However, poly-N-vinylcarbazole
, lacks flexibility, and its coating is hard and brittle, prone to cracking and
The film is easily peeled off, and photoreceptors using this film have poor durability.
is inferior. Therefore, we added plasticizer to improve this drawback.
If it is good, the residual potential will be large in the electrophotographic process.
The residual potential accumulates with repeated use,
The fog gradually increases, damaging the copied image. [0006] In addition, low-molecular organic photoconductive compounds are
Generally, it does not have film-forming ability, so it can be used in combination with an appropriate binder.
In selecting the type of binder, composition ratio, etc.
It is possible to control the physical properties or photosensitive characteristics of the film to some extent.
However, it is preferable in that it has high compatibility with the binder.
The types of organic photoconductive compounds that can be used are limited. In reality
Binder species that can be used in the composition of the photosensitive layer of electrophotographic photoreceptors
There are few types. For example, US Pat. No. 3,189,447
2,5-bis(p-diethylaminophenyl
)-1,3,4-oxadiazole is an electrophotographic photoreceptor.
Binders commonly used as materials for photosensitive layers, such as
Low compatibility with polyester and polycarbonate. vinegar
In other words, at the rate required to adjust the electrophotographic characteristics.
When mixed to form a photosensitive layer, oxidation occurs at a temperature of 50°C or higher.
Diazole crystals begin to precipitate, reducing charge retention and
This method has the disadvantage that electrophotographic properties such as sensitivity and sensitivity deteriorate. In contrast, US Pat. No. 3,820,989
The diarylalkane derivatives described in this issue are binders.
Although there are few compatibility problems with
Repeated transfer in which small particles are repeatedly charged and exposed to light.
When used in electrophotographic photoreceptors, the sensitivity of this photosensitive layer increases.
It has the disadvantage of gradually decreasing. [0009] Also, US Pat. No. 3,274,000,
Special Publication No. 47-36428 has different types of
Phenothiazine derivatives have been described, but none of them are sensitizing.
It has the disadvantages of low luminous intensity and low stability during repeated use.
Ta. [0010] Also, JP-A No. 58-65440, JP-A No. 58-65440,
Described in No. 8-190953 and No. 63-149652.
The charge holding power and sensitivity of the stilbene compounds are comparable.
Although the performance is relatively good, the durability after repeated use is not satisfactory.
It's not something I can afford. [0011] On the other hand, Japanese Patent Application Laid-open No. 175052/1983
, No. 60-174749, No. 62-120346,
No. 64-32265, Japanese Patent Application Publication No. 1-106069,
No. 1-93746, No. 1-274154, etc.
Effects of using distilbene compounds as carrier transport substances
The photoreceptor is a photoreceptor that has almost solved the above drawbacks, but it has complex
Durability when incorporated into photo machines, printers, etc. and used repeatedly
Sex is not satisfying. In particular, the following four points were problematic. 1) In high-speed copying machines with high linear speed, charging, exposure, and removal
Because the power cycle is shortened, residual power is reduced during repeated copying.
The rank will rise significantly. 2) In the case of a copying machine, in the case of repeated copying
In some cases, small white dot-like image defects (called white dots) appear in solid black areas.
) will occur. 3) In the case of a reversal development printer, at a low temperature
Exposure potential (VL) increases and becomes charged due to repeated use.
A defect has been found in which the potential (VH) decreases.
. 4) Image defects in the form of small black dots in white areas (
[0016] In this way, when producing an electrophotographic photoreceptor,
Carrier transport materials with practically satisfactory properties are
The current situation is that it has not been discovered yet. OBJECT OF THE INVENTION The object of the present invention is to provide copiers, printers, etc.
We offer high-sensitivity, highly durable electrophotographic photoreceptors that can be used for
It is about providing. Furthermore, another object of the present invention is to achieve the following (1)
) to (4). (1) In a high-speed copying machine with a high linear speed,
Residual potential does not increase even after repeated charging, exposure, and neutralization.
To provide an electrophotographic photoreceptor. (2) When used in a copying machine, repeated
Even after repeated use, small white dots are missing in the solid black area.
Providing an electrophotographic photoreceptor that does not have defects (called white spots)
to do. (3) Built-in use in a reversal development printer
Even when used repeatedly, the exposure potential (V
L ) does not increase, and the charging potential (VH
) To provide an electrophotographic photoreceptor that does not deteriorate. (4) Small black dot-like image defect in white area
To provide an electrophotographic photoreceptor that does not generate black spots (referred to as black spots).
Things. Structure of the invention and its effects] That is, the present invention has the following features:
Contains a bisstyryl compound represented by general formula [I]
This relates to electrophotographic photoreceptors. [Formula 3] [However, when n≧0 and n=0, R1 is a substitution
Substituted at the 2- or 3-position relative to the amino group
chlorine atom or cyano group, or 2-, 3
- or a fluorine atom substituted at the 4- position,
Bromine atom, iodine atom and halogen having 1 to 4 carbon atoms
It is a functional group selected from alkyl groups. When n≧1
, R1 is 2-, 3- or
A halogen atom, a cyano group or a cyano group substituted at the 4- position
is a halogenated alkyl group having 1 to 4 carbon atoms. R
2 is a lower alkyl group having 1 to 4 carbon atoms, halogen
atoms, cyano groups, and alkyl halides having 1 to 4 carbon atoms
It is a functional group selected from kill groups. The two Cy are different
[Image Omitted] It is a heterocyclic group or a heterocyclic group condensed with a benzene ring. {However, q≧0 and r≧0. two R3, R4
may be different from each other and have 1 to 4 carbon atoms.
Lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms
, halogen atom, cyano group, halogen having 1 to 4 carbon atoms
alkyl group, dialkylamino having 1 to 4 carbon atoms
It is a functional group selected from a group and a dialkyl group. }]
[0024] As the substituent for Cy in general formula [I],
Alkyl groups such as methyl, ethyl, propyl, butyl;
Alkoxy groups such as methoxy, ethoxy, propoxy;
Halogen atoms such as fluorine, chlorine, bromine, and iodine; diethyl
Dialkylamino groups such as amine; diphenethylamine
dialkylamino groups such as; cyano groups; trifluoro
Examples include methyl group. [0025] Further, as the Cy, furyl, thienyl
, pyridyl, quinolyl and other heterocyclic groups are also included,
These may have substituents. And the above substitution
The group may contain up to two groups, but jointly with each other a ring (e.g.
For example, it also includes the case where it forms a six-membered ring). The compound of the above general formula [I] of the present invention is as follows:
It has the characteristics described in A to C, and is an electrophotographic photoreceptor.
It is suitable as a carrier transport material. (A). Bistyrene with substituents in the molecule
Because it is a lyle compound, it has improved sensitivity and durability, and
Also, since fluctuations in charging potential are reduced, copiers and printers
- If you use it repeatedly by incorporating it into
Image defects such as spots, fogging, and decreased density may occur.
No good images are obtained. (B). Moreover, high-speed copiers and printers
If it is installed in a camera, etc. and used repeatedly, it may cause image defects or image defects.
Good images without image defects can be obtained. (C). Since it is a bisstyryl compound, it is easy to synthesize.
be. Specific compounds 1 to 24 of the above general formula [I]
0 are collectively illustrated below. [0030] Below, the bisstyryl compound of general formula [I]
An example of synthesis of things will be explained. (Synthesis Example 1: Synthesis of Exemplified Compound 6) The outline is shown in the figure below.
. ##STR5## A synthesis example is shown below. Combination of diformyl compound 3
The preparation was carried out as follows according to a known method. P-Brom
Aniline 1 (manufactured by Tokyo Kasei Co., Ltd.) (1 molar ratio) and iodoben
Zen (manufactured by Tokyo Kasei Co., Ltd.) (2.5 molar ratio) and potassium carbonate
Mu (manufactured by Kanto Kagaku Co., Ltd.) (2 molar ratio) and copper powder (manufactured by Kanto Kagaku Co., Ltd.)
) (0.2 molar ratio), and the internal temperature was 190 to 210.
The reaction was carried out at ℃ for 50 hours, and after post-treatment, column purification was performed to obtain 4-
Bromotriphenylamine 2 was obtained in a yield of 62% (ur
Mann reaction). 4-bromotriphenylamine 2 (1 mol
ratio) and N,N-dimethylformamide (manufactured by Kanto Kagaku Co., Ltd.)
(4 molar ratio) and phosphorus oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) (
3 molar ratio) and reacted for 24 hours at an internal temperature of 70 to 90°C.
, column purification after post-treatment to obtain N,N-bis-(4-form).
Mylphenyl)-4bromoaniline 3 was obtained in a yield of 54%.
(Vilsmeier reaction). Synthesis of diethyl phosphonate 6 can be carried out by known methods.
In accordance with the law, the following steps were taken: Toluene (Kanto Kagaku Co., Ltd.) under chloroform solvent
) 4 (1 molar ratio) and N-chlorsuccinimide (Higashi
(manufactured by Kyokasei Co., Ltd.) (1 molar ratio) and refluxed for 6 hours.
After the reaction, benzyl chloride 5 was obtained in a yield of 8 after post-treatment.
Obtained at 7%. [0035] Torie phosphite is added to the chloride 5 (1 molar ratio).
Add Chill (manufactured by Kanto Kagaku Co., Ltd.) (1.2 molar ratio) and
React for 10 hours at a temperature of 140 to 160 °C, and after post-treatment
Distillation purification yields diethyl phosphonate 6 in 90% yield.
(phosphonic acid diethylation reaction). Synthesis of CTM is carried out using the compound obtained as described above.
Using the compound as a raw material, the following procedure was performed. N,N-bis
(4-formylphenyl)-4bromoaniline 3 12
．． 5 g (0.033 mol) of benzylphosphonic acid
15.1 g (0.066 mol) of Chill 6 was added to toluene.
The mixture was dissolved in 50 ml of water (manufactured by Wako Pure Chemical Industries, Ltd.). Natoriu
Mumethoxide (manufactured by Kanto Kagaku Co., Ltd.) 3.6 g (0.066
mol) in 50 ml of toluene, cooled on ice, and brought the internal temperature to 2.
This solution was added to the above solution while keeping the temperature below 5°C. [0037] Thereafter, the mixture was stirred at room temperature for 3 hours. water 100
ml, wash the toluene layer with water, and then add sodium sulfate.
Remove water from the toluene layer with lium (manufactured by Kanto Kagaku Co., Ltd.) and dissolve the solution.
The solvent was distilled off, the resulting residue was purified on a silica column, and the
Target Exemplary Compound 7 as yellow-white crystals with a yield of 70%
12.2 g (0.023 mol) was obtained. The melting point was 120-123°C. Former
The elementary analysis values were as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
77.12 5.11
2.61 Calculated value (%): 77.27
4.96 2.6
5 (Synthesis Example 2: Synthesis of Exemplified Compound 30)
Synthesis) In Synthesis Example 1, P-bromoaniline was converted to m-chloroaniline.
Except for replacing phosphorus with P-xylene and replacing toluene with P-xylene.
The exemplified compound was synthesized in the same manner as in Synthesis Example 1, and the exemplified compound was transformed into yellow-white crystals
10.1g (0.020 mol) was obtained with a yield of 60%.
Ta. The melting point was 121-123°C. Former
The elementary analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
84.32 5.09
2.51 Calculated value (%): 84.44
4.96 2.6
5 (Synthesis Example 3: Synthesis of Exemplified Compound 44)
In Synthesis Example 1, P-bromoaniline was converted to P-trifluoromethane.
Replace toluene with tylaniline and P-methoxytoluene
Synthesis was performed in the same manner as in Synthesis Example 1, except that
The compound was obtained as yellow-white crystals in a yield of 65%, 11.0 g (0.
022 mol) was obtained. The melting point was 115-121°C. Former
The elementary analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
81.73 5.91
2.51 Calculated value (%): 81.95
5.73 2.6
5 (Synthesis Example 4: Synthesis of Exemplified Compound 50)
In Synthesis Example 1, P-bromoaniline was converted to P-fluoroaniline.
Except for replacing toluene with mesitylene, the synthetic
Synthesized in the same manner as in Example 1, giving the exemplified compound as yellow-white crystals.
9.3 g (0.018 mol) was obtained with a yield of 54%. The melting point was 110-114°C. Former
The elementary analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
87.01 6.33
2.58 Calculated value (%): 87.15
6.54 2.6
7 [0045] (Synthesis Example 5: Exemplary Compound 14
9) In Synthesis Example 1, P-bromoaniline was
-Same as Synthesis Example 1 except that dichloroaniline was used.
The exemplified compound was synthesized as yellow-white crystals in a yield of 58%.
9.9 g (0.019 mol) was obtained. The melting point was 122-127°C. Former
The elementary analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
73.70 4.22
2.41 Calculated value (%): 73.86
4.38 2.5
3 [0047] The compound of the above general formula [I]
The electrophotographic photoreceptor containing the carrier transport material is as shown in the figure.
The configuration shown in FIGS. 1 to 6 can be adopted. That is, in FIGS. 1 and 2, the conductive support 1
A carrier generation layer 2 containing a carrier generation substance as a main component on top
and a carrier transport substance based on the present invention as a main component.
A photosensitive layer 4 consisting of a laminate with a carrier transport layer 3 is provided.
Let's go. As shown in FIGS. 3 and 4, the photosensitive layer 4 is
It may also be provided via an intermediate layer 5 provided on the conductive support 1.
stomach. When the photosensitive layer 4 has a two-layer structure as described above,
A photoreceptor having excellent electrophotographic properties can be obtained. In addition, in the present invention, as shown in FIGS. 5 and 6,
In order to
A conductive support layer 4 comprising a photosensitive layer 4 dispersed in a layer 6 containing
It may be provided directly on the support 1 or via the intermediate layer 5.
. In addition, in the present invention, as shown in the virtual line in FIG.
In particular, a protective layer 7 may be provided as the outermost layer. The compound of general formula [I] in the present invention is:
Since it has poor coating forming ability by itself, various binders are used.
A photosensitive layer is formed by combining the two. [0054] Any binder can be used here.
However, it is hydrophobic and has a high dielectric constant.
It is preferable to use an electrically insulating film-forming polymer.
Delicious. [0055] Examples of such high molecular weight polymers include, for example,
May include, but are not limited to:
It's not a thing. (P-1) Polycarbonate (P-2
) Polyester (P-3) Methacrylic resin (P-4) Acrylic resin (P-5) Polyvinyl chloride (P-6) Polyvinylidene chloride (P-7) Polystyrene (P-8) Polyvinyl acetate (P-9) Styrene-butadiene copolymer (P-1
0) Vinylidene chloride-acrylonitrile copolymer (P-11) Vinyl chloride-vinyl acetate copolymer (P-11)
-12) Vinyl chloride-vinyl acetate-maleic anhydride
Copolymer (P-13) Silicone resin (P-14) Silicone-alkyd resin (P-1
5) Phenol formaldehyde resin (P-16)
Styrene-alkyd resin (P-17) Poly-
N-vinylcarbazole (P-18) polyvinyl carbazole
Chyral (P-19) Polyvinyl formal [0
[057] These binder resins may be used alone or in combination of two or more.
Can be used as a mixture of the above. CTMs that can be used in combination in the present invention
There are no particular restrictions on the method, but for example, oxazole induction
body, oxadiazole derivatives, thiazole derivatives, thia
Diazole derivatives, triazole derivatives, imidazole
derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivatives, styryl compounds, hydrazo
compounds, pyrazoline derivatives, amine derivatives, oxazo
Ron derivatives, benzothiazole derivatives, benzimidazo
derivatives, quinazoline derivatives, benzofuran derivatives,
Acridine derivatives, phenazine derivatives, aminostilbe
derivatives, poly-N-vinylcarbazole, poly-1-
vinylpyrene, poly-9-vinylanthracene, etc.
. [0059] The CTM used in the present invention is
Excellent ability to transport holes generated during light irradiation to the support side
In addition, combinations with the organic pigments described below used in the present invention
Those suitable for matching are preferred. [0060] For use in the carrier generation layer of the photosensitive layer according to the present invention.
Possible carrier-generating substances include the following:
Can be mentioned. (1) Monoazo dye, bisazo dye, tri-
Azo dyes such as suazo dyes (2) Perylenic acid anhydride, perylenic acid imide, etc.
Ren-based pigments (3) Indigo-based pigments such as indigo and thioindigo (
4) Anthraquinone, pyrenequinone and flavanthro
polycyclic quinones (5) quinacridone dyes (6) bisbenzimidazole dyes (7) induthrone dyes (8) squarerium dyes (9) cyanine dyes (10) azulenium dyes (11) ) Triphenylmethane dye (12) Amorphous silicon (13) Metal phthalocyanine, metal-free phthalocyanine
Which phthalocyanine pigments (14) selenium, selenium-tellurium, selenium-arsenic (15
) CdS, CdSe, (16) Pyrylium salt dye, thiapyrylium salt dye, etc.
can be used alone or as a mixture of two or more
You can also In the electrophotographic photoreceptor according to the present invention,
As CGM, fluorenone bisazo pigment, fluorene
Organic pigments such as redene-based bisazo pigments and polycyclic quinone pigments
is preferably used. In particular, the general formula shown below [
F1 ] fluorenone bisazo pigment, fluorenyl
Dense bisazo pigments and polycyclic quinone pigments are used in the present invention
and significantly improved effects in terms of sensitivity, durability, image quality, etc.
Show results. [0063] Fluorenone type that can be used in the present invention will be described later.
Specific examples of bisazo pigments (F1-1 to F1-24)
However, the invention is not limited thereto. General formula [F1] below that can be used in the present invention
The fluorenone bisazo pigment represented by
For example, Japanese Patent Application No. 62-30486
It is synthesized by a method such as No. 2. Fluorenylidene-based vinyl that can be used in the present invention
The suazo pigment is represented by the general formula [F2] below. Effective for the present invention represented by the general formula [F2]
As a specific example of a bisazo pigment, for example, the structural formula shown below is
List the following (F2-1 to F2-7):
However, this makes it possible to
The pigments are not limited. The polycyclic quinone pigment that can be used in the present invention is
It is represented by the following general formulas [Q1] to [Q3]. [Q1] to [Q3] shown below
Specific examples of polycyclic quinone pigments that can be used in the present invention are given below.
However, it is not limited to this. Ant-Ant represented by the general formula [Q1]
Specific compound examples of Ron pigments (Q1-1 to Q1-6)
The following are listed below. Dibenzpyre represented by the general formula [Q2]
Specific compound examples of quinone pigments (Q2-1 to Q2-
5) is listed below. Pyranthrone represented by the general formula [Q3]
Specific examples of pigment compounds (Q3-1 to Q3-4) are listed below.
The results are as described below. General formulas [Q1] to [Q1] that can be used in the present invention
Q3 ] The polycyclic quinone pigment represented by
can be easily synthesized. Metal-free phthalocyanine that can be used in the present invention
As a pigment, metal-free phthalocyanine with photoconductivity is used.
All derivatives thereof can be used, but for example α
type, β type, τ, τ′ type, η, η′ type, Χ type, and JP-A-Sho
Crystal forms described in No. 62-103651 and derivatives thereof, etc.
can be used. Especially when using τ, Χ, K/R-Χ types,
It is desirable that For Χ-type metal-free phthalocyanine, the United States
Described in Patent No. 3,357,989, τ-type metal-free
Regarding phthalocyanine, see JP-A-58-182639.
There is a description in . [0075] K/R-X type is disclosed in Japanese Patent Application Laid-Open No. 103651/1986.
As stated in the issue, CuKα is resistant to 1.541 Å X-rays.
At the Bragg angle (2θ±0.2 degrees), 7.
7, 9.2, 16.8, 17.5, 22.4,
It has a major peak at 28.8 degrees and a peak of 9.2 degrees.
The peak intensity ratio of 16.8 degrees to the peak intensity is 0.8
~1.0 and 28.8 for 22.4 degrees
A film characterized by a peak intensity ratio of 0.4 or more.
It is talocyanin. Oxytitanyl phthalo usable in the present invention
Cyanine is represented by the general formula [TP] below. [0077] Those that can be used in the present invention are shown below.
Different crystal forms are known that have been disclosed in patents.
. For example, JP-A-61-239248, JP-A No. 62-670
No. 943, No. 62-272272, No. 63-1161
No. 58 or No. 64-17066, JP-A-2-282
No. 65, No. 2-215860, and the like. Dispersion medium for organic pigments that can be used in the present invention
There are known dispersion media such as methyl ethyl ketone. [0079] In the present invention, the photosensitive layer may contain one or two types.
The above known electron-accepting substances can be contained.
Ru. The addition ratio of the electron-accepting substance used in the present invention is determined by weight ratio.
Organic pigment that can be used: Electron accepting substance = 100:
0.01-200, preferably 100:0.1
~100. In addition, the addition ratio of electron-accepting substances is
Weight ratio of total CTM:electron-accepting substance=100:0
．． 01-100, preferably 100:0.1-
It is 50. [0080] Also, CGM (carrier generating material) is contained in the photosensitive layer.
Organic amines are added to improve the charge generation function of
It is particularly preferred to add secondary amines.
Yes. These compounds are disclosed in JP-A No. 59-218447,
It is described in No. 62-8160. [0081] In addition, in the photosensitive layer, ozone deterioration prevention
For example, the antioxidant of JP-A-63-18354
can be added. The amount of antioxidant added is CTM
0.1 to 100 parts by weight per 100 parts by weight, preferably
Preferably 1 to 50 parts by weight, particularly preferably 5 to 25 parts by weight
Department. [0082] The photoreceptor according to the present invention also includes other necessary components.
Contains ultraviolet absorber, etc. to protect the photosensitive layer as necessary.
It may also contain a dye for color sensitivity correction. [0083] An intermediate layer may be provided between the photosensitive layer and the support.
However, this intermediate layer can be used as an adhesive layer, blocking layer, etc.
It's something that works. In the present invention, the photosensitive layer is composed of two layers as shown in FIG.
When configured, the CGL (carrier generation layer) is electrically conductive.
directly on the support or CTL (carrier transport layer)
If necessary, add an adhesive layer or blocking layer, etc.
After providing an intermediate layer, it can be formed by the following method.
can. (1) Vacuum evaporation method (2) CGM was dissolved in a suitable solvent
Method of applying the solution (3) CGM by ball mill or sandog
Required as fine particles in dispersion medium by liner etc.
Depending on the situation, apply a dispersion obtained by mixing and dispersing with a binder.
how to. Specifically, vacuum evaporation, sputtering
Vapor phase deposition methods such as gluing, CVD, dipping, and spraying
Application methods such as ray, blade, and roll methods may be used arbitrarily.
It will be done. The thickness of the CGL formed in this way is
, preferably 0.01 μm to 5 μm, more preferably
Preferably, it is 0.05 μm to 3 μm. [0090] Also, regarding CTL, similar to CGL,
It can be formed by The thickness of CTL depends on the required
Although it can be changed depending on the size, it is usually 5 μm to 60 μm.
is preferred. [0091] The composition ratio in this CTL is based on the composition ratio of the present invention.
0.1 to 5 parts by weight of binder per 1 part by weight of CTM
It is preferable to disperse CGM in the form of fine particles.
When forming the photosensitive layer 4, add a buffer to 1 part by weight of CGM.
It is preferable to use indica in an amount of 5 parts by weight or less. In addition, when CGL is configured as a dispersed type in a binder,
If the binder is 5 parts by weight or more per 1 part by weight of CGM,
It is preferable to use the following range. The electrophotographic photoreceptor according to the present invention is as described above.
As is clear from the examples described later,
, has excellent charging characteristics, sensitivity characteristics, image forming characteristics, etc.
Particularly durable, with little fatigue deterioration even after repeated use.
It has excellent properties. Furthermore, the electrophotographic photoreceptor according to the present invention
In addition to photocopy machines, lasers, cathode ray tubes (CRTs), and
Photoreceptor of a printer that uses a photodiode (LED) as a light source
It can also be widely used in other application fields. Also, books
In addition to such photoreceptors, the invention also includes EL (electroluminescence).
It can also be applied to other applications such as (minescence), etc. [Example] Hereinafter, specific examples of the present invention will be described.
However, this does not limit the embodiments of the present invention.
It's not something you can do. Example 1 ε-amino-caproic acid, adipic acid and N-(β-amino-caproic acid)
Monomers with a ratio of 1:1:1 (minoethyl)piperazine
30g of polyamide copolymerized with the composition is heated to 50℃
800 ml methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.)
) was added to 200 ml. After that, an 80mm diameter aluminum
Dip coated onto a mini-drum, 0.6 μm thick
formed a layer. Next, as a CGM, fluorenone-based disa
20g of pigment (exemplary compound F1-23) and binder
Polyvinyl butyral resin S-LEC BX-1
(Manufactured by Sekisui Chemical Co., Ltd.) 10g methyl ethyl ketone (Kanto Kagaku)
Dissolve in 1000 ml (manufactured by Gakusha, EL standard), and
Milling was performed for 24 hours in a mill to obtain a CGL coating solution. This was coated by dip coating on the above intermediate layer to give a thickness of 0.2 μm.
GL was formed. Thereafter, 140 g of the Exemplified Compound 14
and polycarbonate resin “Iupilon Z-200” (
165g (manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 1,2-dichloro
Dissolve in 1000 ml of special grade ethane (manufactured by Kanto Kagaku Co., Ltd.),
A CTL coating liquid was obtained. After applying this by dip coating on the above CGL, 100%
It was dried at ℃ for 1 hour to form a 23 μm thick CTL. In this way, the intermediate layer-CGL-CTL are sequentially laminated.
A photoreceptor 1 was prepared. Examples 2 to 10 In Example 1, CGM and CTM were exemplified as shown in Table 1 below.
Photoreceptors 2 to 10 were prepared in the same manner as in Example 1 except that they were made into composites.
It was created. Comparative Examples 1 and 2 As shown in Table 1 below, the CTM of Example 1 was compared as shown below.
Comparative exposure was carried out in the same manner as in Example 1 except that Compounds 1 and 2 were used.
created a body. Example 11 The intermediate layer was formed in the same manner as in Example 1. [0102] As CGM, polycyclic quinone pigments (examples)
compound; Q1-3) 20g and poly as a binder.
Carbonate resin C-1300 (manufactured by Teijin Chemicals) 10g
Dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.)
Milled with a ball mill for 30 hours and coated with CGL.
I got the liquid. This was applied by dip coating on the above intermediate layer to give a 0.6
A CGL with a thickness of μm was formed. Next, using CTM as exemplified compound 21,
On the outside, CTL was laminated in the same manner as in Example 1, and photoreceptor 11 was fabricated.
accomplished. Examples 12 to 20 In Example 11, CGM and CTM were as shown in Table 2 below.
Photoreceptor 1 was prepared in the same manner as in Example 11 except that the compound shown was used.
2 to 20 were created. Comparative Examples 3 to 4 As shown in Table 2 below, CTM in Example 11 was used as a comparative compound.
A comparative photoreceptor was prepared in the same manner as in Example 11 except that the values were changed to 3 to 4.
3-4 were created. Example 21 Polyvinyl butyral resin (S-LEC BX-1, Sekisui Co., Ltd.
(manufactured by Kagakusha) 12g to 1000ml of methyl ethyl ketone
After dissolving, Exemplified Compound Q1-3;5 as CGM
．． 7 g and 0.5 g of exemplified compound F1-23 were mixed.
, and dispersed with a sand grinder for 12 hours. [0107] This was dip coated onto the intermediate layer described in Example 1.
to form CGL, and further use Exemplified Compound 37 in Table 3.
A CTL was formed in the same manner as in Example 1, and the photoreceptor 21
It was created. Examples 22 to 30 In Example 21, CGM and CTM were as shown in Table 3 below.
Photoreceptor 2 was prepared in the same manner as in Example 21 except that the compound shown was used.
2 to 30 were created. Comparative Examples 5 and 6 As shown in Table 3 below, CTM in Example 21 was used as a comparative compound.
A comparative photoreceptor was prepared in the same manner as in Example 21 except that the values were changed to 5 to 6.
5-6 were created. Example 31 50 g of the polyamide used in Example 1 was heated to 50°C.
To 800 ml methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.)
and dissolved. After cooling to room temperature, 1-butanol
200 ml of special grade (manufactured by Kanto Kagaku Co., Ltd.) was added. after that,
Dip coating onto an aluminum drum with a diameter of 80 mm, and
．． An intermediate layer of 5 μm was formed. [0111] Next, as CGM, τ-type metal-free phthalocia
40g of Nin (τ-Pc) was mixed with silicone resin “KR-52”.
40'' (solid content 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.) 200 g
Dissolved methyl ethyl ketone EL standard (manufactured by Kanto Kagaku Co., Ltd.)
In addition to 2000ml, use a sand grinder for 4 hours.
The mixture was dispersed to obtain a CGL coating liquid. Place this on the above middle layer
A CGL with a thickness of 0.4 μm was formed by dip coating. [0112] Then, 135 g of Exemplified Compound 5 and polycarbonate
carbonate “Iupilon Z-200” (Mitsubishi Gas Chemical
Co., Ltd.) 165 g of 1,2-dichloroethane special grade (
(manufactured by Kanto Kagaku Co., Ltd.) and dissolve in 1000 ml of CTL coating liquid.
I got it. After applying this on the above CGL by dip coating, it was heated at 100℃.
Drying was performed for 1 hour to obtain a CTL with a thickness of 22 μm. middle class
A photoreceptor was created by laminating CGL and CTL in this order.
Ta. Examples 32 to 40 In Example 31, CTM was converted to exemplified compounds as shown in Table 4 below.
Photoreceptors 32 to 40 were prepared in the same manner as in Example 31 except that
It was created. Comparative Examples 7-8 As shown in Table 4 below, CTM in Example 31 was used as a comparative compound.
A comparative photoreceptor was prepared in the same manner as in Example 31 except that the values were changed to 1 to 2.
It was created. Example 41 Using X-type metal-free phthalocyanine (X-Pc) in CGM
The intermediate layer-CGL-CT was prepared in the same manner as in Example 1 except that
A photoreceptor was prepared by sequentially laminating L. Examples 42 to 50 In Example 41, CTM was converted to exemplified compounds as shown in Table 5 below.
Photoreceptors 42 to 50 were prepared in the same manner as in Example 41 except that
It was created. Comparative Examples 9-10 As shown in Table 5 below, CTM in Example 41 was used as a comparative compound.
Comparative photoreceptor was prepared in the same manner as in Example 41 except that 3 to 4 were used.
It was created. Example 51 Y-type oxytitanium phthalocyanine (Y-T
iOPC) [Journal of Electrophotography Society 250 (2), 29 (
2), 1990] in the same manner as in Example 1.
A photoreceptor made by sequentially laminating an intermediate layer, CGL, and CTL.
It was created. Examples 52 to 60 In Example 51, CTM was converted to exemplified compounds as shown in Table 6 below.
Photoreceptors 52 to 60 were prepared in the same manner as in Example 51 except that
It was created. Comparative Examples 11-12 As shown in Table 6 below, CTM in Example 51 was used as a comparative compound.
Comparative photoreceptor was prepared in the same manner as in Example 51 except that 5 to 6 were used.
It was created. Example 61 Except for using fluorenylidene-based azo CGM as CGM
, In the same manner as in Example 1, the intermediate layer-CGL-CTL were sequentially formed.
A photoreceptor made of laminated layers was created. Examples 62 to 70 In Example 61, CGM and CTM were exemplified as shown in Table 7 below.
Photoreceptor 62 was prepared in the same manner as in Example 61 except that a compound was used.
~70 were created. Comparative Examples 13-14 As shown in Table 7 below, CTM in Example 61 was used as a comparative compound.
A comparative photoreceptor was prepared in the same manner as in Example 61 except that the values were changed to 1 to 2.
It was created. [0124]
Table-1 Example No.
Photoreceptor No. CGM
CTM ──────────────
────────────────────
Example 1 Photoreceptor 1 Compound F1 −
23 Exemplary Compounds 14 Example 2
Photoreceptor 2 Compound Example
Compound 2 Example 3 Photosensitivity
Body 3 Compound 〃 Exemplary compound
5 Example 4 Photoreceptor 4
Compound 〃 Exemplary compound 8
Example 5 Photoreceptor 5 Compound
〃 Exemplary compound 11 Example 6
Photoreceptor 6 Compound F1-1 Example
Compound 140 Example 7
Light body 7 Compound 〃 Exemplary compound
153 Example 8 Photoreceptor 8
Compound 〃 Exemplary compound 154
Example 9 Photoreceptor 9 Compound
F1-7 Exemplary Compound 160 Example
10 Photoreceptor 10 Compound F1 -1
6 Exemplary Compound 206 Comparative Example 1
Comparative photoreceptor 1 Compound F1-23 Comparative compound
1 Comparative Example 2 Comparative Photoreceptor 2
Compound F1-23 Comparative compound 2 012
5]
Table-2 Example No.
Photoreceptor No. CGM
CTM ──────────────
────────────────────
Example 11 Photoreceptor 11 Compound Q1
-3 Exemplary compound 21 Example 12
Photoreceptor 12 Compound 〃
Exemplary compound 18 Example 13
Photoreceptor 13 Compound Example
Compound 24 Example 14
Photoreceptor 14 Compound 〃 Exemplary compound
Object 27 Example 15 Photoreceptor
15 Compounds Exemplary compounds
30 Example 16 Photoreceptor 16
Compound 〃 Exemplary compound 67
Example 17 Photoreceptor 17
Compound 〃 Exemplary compound 164
Example 18 Photoreceptor 18 Compound
〃 Exemplary compound 170
Example 19 Photoreceptor 19 Compound
〃 Exemplary compound 223 Example 2
0 Photoreceptor 20 Compound
Exemplary compound 232 Comparative example 3
Comparative photoreceptor 3 Compound Comparative compound
Product 3 Comparative Example 4 Comparative Photoreceptor 4
Compound 〃 Comparative compound 4 012
6]
Table-3 Example No. Photoreceptor N
o. CGM
CTM────────────────
────────────────────Example 21
Photoreceptor 21 Compound Q1-3
F1-23 Exemplary compound 37 Example 22
Photoreceptor 22 Compound
Exemplary compound 34 Example 23
Photoreceptor 23 Compound
Exemplary compound 36 Example 24
Photoreceptor 24 compound
〃 Exemplary compound 40 Example 25
Photoreceptor 25 Compound
〃 Exemplary compound 45 Example 2
6 Photoreceptor 26 Compound Q1-3
F1-1 Exemplary compound 46 Example 27
Photoreceptor 27 Compound
Exemplary compound 48 Example 28
Photoreceptor 28 Compound Q1 -3 F1
-1 Exemplary compound 163 Example 29
Photoreceptor 29 Compound Q1 -3 F1 -7
Exemplary compound 165 Example 30 Photoreceptor 3
0 Compound Q1 -3 F1 -16 Examples
Compound 209 Comparative Example 5 Comparative Photoreceptor 5 Compound
Compound Q1-3 F1-23 Comparative compound 5 ratio
Comparative Example 6 Comparative Photoreceptor 6 Compound
〃 Comparative compound 6 0127
]
Table-4 Example No. photosensitive
Body No. CGM
CTM──────────────────
──────────────────── Example 3
1 Photoreceptor 31 Compound τ-type gold-free
Genus Lid Exemplary Compound 5
B
Cyanine Example 32 Photoreceptor 32
Compound 〃 Exemplary compound
Object 2 Example 33 Photoreceptor 33
Compound 〃 Exemplary compound
Object 14 Example 34 Photoreceptor 34
compound 〃 exemplification
Compound 9 Example 35 Photoreceptor 35
compound 〃 exemplification
Compound 11 Example 36 Photoreceptor 36
Compound Example
Compound 153 Example 37 Photoreceptor 37
Compound Example
Compound 155 Example 38 Photoreceptor 3
8 Compound 〃
Exemplary compound 167 Example 39 Photoreceptor
39 Compound 〃
Exemplified Compound 216 Example 40 Photosensitivity
body 40 compound
Exemplified Compound 232 Comparative Example 7 Comparative Sensitivity
Body 7 Compound 〃 Ratio
Comparative compound 1 Comparative example 8 Comparative photoreceptor 8
Compound 〃 Comparative compound
20128]
Table-5 Example No. photosensitive
Body No. CGM
CTM──────────────────
────────────────Example 41
Photoreceptor 41 Compound X-type metal-free
Exemplary compound 30
Phthalo
Cyanine Example 42 Photoreceptor 42
Compound 〃 Exemplary compound
Object 21 Example 43 Photoreceptor 43
Compound X-type metal-free exemplified compound
25
Phthalocyanine Example 44
Photoreceptor 44 Compound
Exemplified Compound 27 Example 45
Photoreceptor 45 Compound
Exemplary compound 32 Example 46
Photoreceptor 46 Compound
Exemplary compound 63 Example 4
7 Photoreceptor 47 Compound
〃 Exemplary compounds 80 Examples
48 Photoreceptor 48 Compound
〃 Exemplary compound 137 implementation
Example 49 Photoreceptor 49 Compound
〃 Exemplary compound 146 fruit
Example 50 Photoreceptor 50 Compound
〃 Exemplary compound 223
Comparative Example 9 Comparative Photoreceptor 9 Compound
〃 Comparative compound 3 Comparative example 1
0 Comparative photoreceptor 10 Compound
Comparative compound 4
Table-6 Example No. photosensitive
Body No. CGM
CTM──────────────
──────────────────────Example
51 Photoreceptor 51 Compound Y-type O
Oxytitanium Exemplary Compound 46
　　　　　　　　　　　　　　　　　　　　　　　　　
Phthalocyanine Example 52 Photoreceptor 52
Compound 〃
Exemplified Compound 34 Example 53
Photoreceptor 53 Compound
Exemplary compound 37 Example 54
Photoreceptor 54 Compound
Exemplary compounds 40 fruits
Example 55 Photoreceptor 55 Compound
〃 Exemplary compounds
43 Example 56 Photoreceptor 56
Compound 〃
Exemplary compound 136 Example 57 Photoreceptor 57
Compound 〃
Exemplary compound 163 Example 58
Photoreceptor 58 Compound
Exemplary compound 165 Example 59
Photoreceptor 59 Compound
Exemplified compound 209 fruit
Example 60 Photoreceptor 60 Compound
〃 Exemplary compounds
232 Comparative Example 11 Comparative Photoreceptor 11 Compound
〃 Comparison
Compound 5 Comparative Example 12 Comparative Photoreceptor 12
Compound 〃
Comparative compound 6
Table-7 Example No.
Photoreceptor No. CGM
CTM ────────────────────
──────────── Example 61
Photoreceptor 61 Compound F2-6 Exemplary compound
Object 5 Example 62 Photoreceptor 62
Compound 〃 Exemplary compound 2
Example 63 Photoreceptor 63 Compound
〃 Exemplary compound 8 Example 6
4 Photoreceptor 64 Compound
Exemplary compound 11 Example 65
Photoreceptor 65 Compound Example
Compound 14 Example 66 Photoreceptor
66 Compound 〃 Exemplary compound 1
41 Example 67 Photoreceptor 67
Compound 〃 Exemplary compound 154
Example 68 Photoreceptor 68 Compound
〃 Exemplary compound 155 Example 6
9 Photoreceptor 69 Compound F2-3
Exemplary compound 160 Example 70
Photoreceptor 70 Compound F2-5 Exemplary compound
198 Comparative Example 13 Comparative Photoreceptor 13
Compound F2-6 Comparative compound 1 Comparative example
14 Comparative photoreceptor 14 Compound
Comparative Compound 2 (Evaluation Example 1)
Modified copying machine U-Bix5076 manufactured by Nika Co., Ltd. (charged electrode)
was changed to negative charge, exposure amount was 4.65 lux), and the linear velocity was changed to
3 stages of 240, 330, and 440 mm/sec
Residual potential after repeated charging and exposure 20,000 times
Vr was measured. The results are shown in Tables 8 to 10 below.
The photoreceptor using the CTM of the present invention uses a comparative compound.
When the linear velocity is increased, the residual potential is larger than that of the conventional photoreceptor.
It showed excellent high speed performance. Note that the initial blank potential (V
w) were as shown in Tables 8 to 10 below. (Evaluation Example 2) Same as that used in Evaluation Example 1
Using a modified Konica copier U-Bix5076
, 100,000 continuous copy tests using A4 recycled paper
went. The results are shown in Tables 11 to 13 below.
The photoreceptor using the compound of this patent has good image quality up to 100,000 cycles.
However, the photoreceptor using the comparative photoreceptor was used 20,000 to 30,000 times.
Several white spots appeared on the solid black part. In addition, Shiro Pochi's review
The value is determined by visually observing the number of white spots that occur on an A4 solid black image.
I counted. The results are shown in Tables 11 to 13 below. (Evaluation Example 3) Konica Digital Copy
U-Bix8028 was used at room temperature (25℃) and low temperature (
10°C), unexposed part potential VH, exposed part potential V
L was measured. The results are shown in Tables 14 to 17 below. (Evaluation Example 4) Same as that used in Evaluation Example 3
Konica's digital copy U-Bix8028,
Load the developing device and print out the image several times to make the white background of the copied image
The black spots in the area were evaluated. The results are in Tables 18 to 21 below.
Indicated. [0135] The evaluation of black spots was performed using the image analysis device "OMM".
Black spots were detected using Nikon 300 model (manufactured by Shimadzu Corporation).
Measure the particle size and number of points, and find
Judgment was made based on the number of black spots per cm2. The criteria for black spot evaluation are as shown in the table below. [0136] Furthermore, if the result of black spot determination is ◎ or ○, it is practical.
However, △ may not be suitable for practical use, and × may not be suitable for practical use.
unsuitable for use. [0137]
Table-8
Initial cycle 20,000 times at the following linear speed
Vr(v) after return
Blank paper potential Photoreceptor No. Vw(
v) 240mm/sec 330mm/
sec 440mm/sec
Repeat with
Then repeat and repeat ──
──────────────────────────
───── Photoreceptor 1 48
10 14
18 Photoreceptor 2
53 12
17 24
Photoreceptor 3 49 1
1 15
19 Photoreceptor 4 54
13 18
26 Photoreceptor 5
55 14
19 27
Photoreceptor 6 52 12
16
23 Photoreceptor 7 50
11 15
20 Photoreceptor 8
52 12
17 23
Photoreceptor 9 48 10
14 1
8 Photoreceptor 10 56
15 19
28 Comparative photoreceptor 1
75 22
48 88 Comparative sensitivity
body 2 68 17
43 77 0138]
Table-9
Initial cycle 20,000 times at the following linear speed
Vr(v) after return
Blank paper potential Photoreceptor No. Vw(
v) 240mm/sec 330mm/
sec 440mm/sec
Repeat with
Then repeat and repeat ──
──────────────────────────
───── Photoreceptor 11 97
13 16
28 Photoreceptor 12
103 14
18 30
Photoreceptor 13 101
13 17
29 Photoreceptor 14 1
05 15 1
9 34 Photoreceptor
15 94 12
15 26
Photoreceptor 16 93
11 14
25 Photoreceptor 17
92 10
13 23 feeling
Light body 18 90 9
12 21
Photoreceptor 19 91
9 13
22 Photoreceptor 20
93 11
13 23 Comparison
Light body 3 125 18
44 88
Comparative photoreceptor 4 118
16 41
85 0139]
Table-10
Initial: 20,000 repetitions at the following linear speed
Vr(v) after repetition
Blank paper potential Photoreceptor No. Vw
(v) 240mm/sec 330mm
/sec 440mm/sec
Repeat
repeat with return repeat with repeat ─
──────────────────────────
────── Photoreceptor 21 7
1 13 17
23 Photoreceptor 2
2 73 15
19 26
Photoreceptor 23 72
14 17
24 Photoreceptor 24
70 12
16 22 Photosensitivity
body 25 72 14
18 24
Photoreceptor 26 69
11 15
21 Photoreceptor 27
74 17
21 29
Photoreceptor 28 67 9
14 1
9 Photoreceptor 29 68
10 15
20 Photoreceptor 30
73 15
19 25 ratio
Comparison photoreceptor 5 98 19
42 87
Comparative photoreceptor 6 82
17 40
78 0140
Table-11 Photoreceptor No.
After 10,000 times After 50,000 times After 100,000 times
Number of white spots
Number of white dots Number of white dots ───
──────────────────────
Photoreceptor 1 0
0 0
Photoreceptor 2 0
0 0 Photoreceptor
3 0 0
0 Photoreceptor 4
0 0
1 photoreceptor 5 0
1 2
Photoreceptor 6 0
0 0
Photoreceptor 7 0
0 0 Photoreceptor
8 0 0
0 Photoreceptor 9
0 0
0 photoreceptor 10
0 1 2
Comparative photoreceptor 1 6
22 42
Comparative photoreceptor 2 4 2
0 39 0141]
Table-12 Photoreceptor No.
After 10,000 times After 50,000 times After 100,000 times
Number of white spots
Number of white dots Number of white dots ───
──────────────────────
Photoreceptor 11 0
0 1
Photoreceptor 12 0
1 2 feeling
Light body 13 0 0
1 Photoreceptor 14
0 1
2 Photoreceptor 15
0 0
0 Photoreceptor 16
0 0 0
Photoreceptor 17 0
0 0
Photoreceptor 18 0
0 0
Photoreceptor 19 0 0
0 Photoreceptor 2
0 0 0
0 Comparative photoreceptor 3
8 24
48 Comparative photoreceptor 4 6
19 43 0142]
Table-13 Photoreceptor No.
After 10,000 times After 50,000 times After 100,000 times
Number of white spots
Number of white dots Number of white dots ───
──────────────────────
Photoreceptor 21 0
0 0
Photoreceptor 22 0
1 2 feeling
Light body 23 0 0
0 Photoreceptor 24
0 0
0 Photoreceptor 25
0 0
0 Photoreceptor 26
0 0 0
Photoreceptor 27 0
1 3
Photoreceptor 28 0
0 0
Photoreceptor 29 0 0
0 Photoreceptor 3
0 0 1
2 Comparative photoreceptor 5
5 21
39 Comparative photoreceptor 6 3
18 37 0143]
Table-14
Room temperature (25℃)
Low temperature (10℃) Photoreceptor N
o.
VH(v) VL(v) VH(v) VL
(v) ────────────
──────────── Photosensitivity
Body 31 701 106 7
03 108 Photoreceptor
32 698 111 70
0 115 Photoreceptor 3
3 705 101 707
103 Photoreceptor 34
697 113 695
118 Photoreceptor 35
690 116 693
122 Photoreceptor 36
706 100 701
101 Photoreceptor 37
710 99 711
99 Photoreceptor 38
712 97 713
99 Photoreceptor 39
695 114 693 1
20 Photoreceptor 40 7
02 108 699 11
1 Comparative photoreceptor 7 705
126 683 178
Comparative photoreceptor 8 702 1
21 684 170 0144]
Table-15
Room temperature (25℃)
Low temperature (10℃) Photoreceptor N
o.
VH(v) VL(v) VH(v) VL
(v) ────────────
──────────── Photosensitivity
Body 41 717 104 7
15 105 Photoreceptor
42 715 102 71
3 101 Photoreceptor 4
3 697 110 695
115 Photoreceptor 44
695 109 692
114 Photoreceptor 45
692 115 689
119 Photoreceptor 46
701 104 700
102 Photoreceptor 47
720 100 718
101 Photoreceptor 48
702 105 704
103 Photoreceptor 49
718 101 720 1
00 Photoreceptor 50 7
09 108 701 11
3 Comparative photoreceptor 9 709
124 680 177
Comparative photoreceptor 10 707
121 685 171 0145]
Table-16
Room temperature (25℃) Low
Temperature (10℃) Photoconductor No.
．．
VH(v) VL(v) VH(v) VL(
v) ──────────────
────────── Photoreceptor
51 708 52 71
0 51 Photoreceptor 5
2 696 54 695
56 Photoreceptor 53
710 50 708
51 Photoreceptor 54
703 52 704
52 Photoreceptor 55
692 55 690
58 Photoreceptor 56
704 52 702
53 Photoreceptor 57
717 49 720
48 Photoreceptor 58
713 48 711
48 Photoreceptor 59 6
93 56 691 5
9 Photoreceptor 60 70
5 51 706 52
Comparative photoreceptor 11 718
63 685 91
Comparative photoreceptor 12 714
60 682 82 0146]
Table-17
Room temperature (25℃)
Low temperature (10℃) Photosensitive
Body No.
VH(v) VL(v) VH(v)
VL(v) ──────────
──────────────
Photoreceptor 61 711 103
710 104 feeling
Light body 62 702 109
700 113 Photosensitivity
Body 63 708 105 7
05 107 Photoreceptor
64 701 108 69
9 112 Photoreceptor 6
5 698 112 696
117 Photoreceptor 66
712 101 709
103 Photoreceptor 67
714 99 715
101 Photoreceptor 68
715 98 714
100 Photoreceptor 69
711 102 709
104 Photoreceptor 70
699 110 700
114 Comparative photoreceptor 13 71
1 125 688 156
Comparative photoreceptor 14 718
119 684 147 0147]
Table-18
20,000 copies 50,000 copies 1
After 00,000 copies of photoconductor used
after after
black spot format
Fixed Black spot determination Black spot determination ──
──────────────────────────
─── Photoreceptor 31
◎ ◎
◎ Photoreceptor 32
◎ ○
○ Photoreceptor 33
◎ ◎
◎ Photoreceptor 34
◎ ○
○ Photoreceptor 35
◎ ○
○ Photoreceptor 36
◎ ◎
○ Photoreceptor 37
◎ ◎
◎ Photoreceptor 38
◎ ◎
◎ Photoreceptor 39
◎ ○
○ Photoreceptor 40
◎ ◎
○ Comparative photoreceptor 7 ○
△ ×
Comparative photoreceptor 8 ○
△ × [0148]
Table-19
20,000 copies 50,000 copies 1
After 00,000 copies of photoconductor used
after after
black spot format
Fixed Black spot determination Black spot determination ──
──────────────────────────
─── Photoreceptor 41
◎ ◎
◎ Photoreceptor 42
◎ ◎
◎ Photoreceptor 43
◎ ◎
○ Photoreceptor 44
◎ ○
○ Photoreceptor 45
◎ ○
○ Photoreceptor 46
◎ ◎
◎ Photoreceptor 47
◎ ◎
◎ Photoreceptor 48
◎ ◎
○ Photoreceptor 49
◎ ◎
◎ Photoreceptor 50
◎ ○
○ Comparative photoreceptor 9 ○
△ ×
Comparative photoreceptor 10 ○
△ × [0
149]
Table-20
20,000 copies 50,000 copies 1
After 00,000 copies of photoconductor used
after after
black spot format
Fixed Black spot determination Black spot determination ──
──────────────────────────
─── Photoreceptor 51
◎ ◎
◎ Photoreceptor 52
◎ ◎
○ Photoreceptor 53
◎ ◎
◎ Photoreceptor 54
◎ ◎
◎ Photoreceptor 55
◎ ○
○ Photoreceptor 56
◎ ◎
◎ Photoreceptor 57
◎ ◎
◎ Photoreceptor 58
◎ ◎
◎ Photoreceptor 59
◎ ○
○ Photoreceptor 60
◎ ◎
◎ Comparative photoreceptor 11 △
△
× Comparative photoreceptor 12 ○
△ ×【
0150]
Table-21
20,000 copies 50,000 copies 1
After 00,000 copies of photoconductor used
after after
black spot format
Fixed Black spot determination Black spot determination ──
──────────────────────────
─── Photoreceptor 61
◎ ◎
◎ Photoreceptor 62
◎ ◎
○ Photoreceptor 63
◎ ◎
◎ Photoreceptor 64
◎ ○
○ Photoreceptor 65
◎ ○
○ Photoreceptor 66
◎ ◎
◎ Photoreceptor 67
◎ ◎
◎ Photoreceptor 68
◎ ◎
◎ Photoreceptor 69
◎ ◎
◎ Photoreceptor 70
◎ ○
○ Comparative photoreceptor 13 △
×
× Comparative photoreceptor 14 ○
△ ×【
[0151] As mentioned above, electrophotographic sensitization based on the present invention
The body can be incorporated into a copier, printer, etc. and used repeatedly.
When using high sensitivity, white spots, black spots, fogging, and decreased density can be detected.
It is possible to obtain good images without image defects such as
It will be done. [0152] Furthermore, the electrophotographic photoreceptor according to the present invention has a high
Even if it is installed in a high-speed copier or printer and used repeatedly
, a high quality product with a small residual potential and no image defects or poor image quality.
A good image can be obtained. Example 71 Next, unlike the above example, the present invention was
An example in which the present invention is applied to luminescence will be described. [0154] Transparent electrodes (inner electrodes) formed on a glass substrate
500 as a charge injection layer on top of the (dium-tin oxide layer)
Exemplary compound (2) was vapor-deposited to a thickness of
Nolinol A1 complex (Alq3) as an organic fluorescent layer
The negative electrode was deposited to a thickness of 600 Å, and a negative electrode was placed on top of it.
Then, a magnesium/aluminum alloy was deposited. [0155] The emission characteristics of the obtained organic thin film EL device were investigated.
As a result, the light emission of 0.04mW/cm2 is 4mA/
Obtained in cm2. The emitted light color was yellow-green. [0156] Specific compounds of general formula [I] are listed below.
Classified into general formula [Ia] and general formula [Ib], Table-22
and is illustrated in Table-23. General formula [Ia] [Chemical formula 6]
Table-22 No. R1
(R2)n (R31)q1
(R32)q2────────────
──────────────────────1
2-FH
H H2
3-F 〃
〃 〃3
4-F 〃
〃 〃4
2-Br 〃
〃 〃5 3-
Br 〃 〃
〃6 4-Br
〃 〃
〃7 2-I
〃 〃
〃8 3-I
〃 〃
〃9 4-I
〃 〃
〃10 2-CF3
〃 〃
〃11 3-CF3
〃 〃
〃12 4-CF3
〃 〃
〃13 2-Cl
〃 〃
〃14 3-Cl
〃 〃
〃15 2-CN 〃
〃
〃16 3-CN 〃
〃
〃17 2-F 〃
4-CH3
4-CH318 3-F
〃 〃
〃19 4-F
〃 〃
〃20 2-Br
〃 〃
〃21 3-Br
〃 〃
〃22 4-Br 〃
〃
〃23 2-I 〃
〃
〃24 3-I 〃
〃
〃25 4-I 〃
〃
〃26 2-CF3H
4-CH3
4-CH3 27 3-CF3 〃
〃 〃2
8 4-CF3 〃
〃 〃29
2-Cl 〃
〃 〃30
3-Cl 〃
〃 〃31
2-CN〃
〃 〃32
3-CN〃
〃 〃33
2-F 〃
4-OCH3 4-OCH334
3-F 〃
〃 〃35
4-F 〃
〃 〃36
2-Br 〃
〃 〃37
3-Br 〃
〃 〃38
4-Br 〃
〃 〃39
2-I 〃
〃40 3-I
〃 〃
〃41 4-I
〃 〃
〃42 2-CF3
〃 〃
〃43 3-CF3 〃
〃
〃44 4-CF3 〃
〃
〃45 2-Cl 〃
〃
〃46 3-Cl 〃
〃 〃
47 2-CN 〃
〃 〃4
8 3-CN〃
〃 〃49
2-F 〃
3,5-di-CH3 3,5-di
-CH350 4-F
〃 〃
〃51 2-Br 〃
〃
〃52 4-Br 〃
〃
〃53 4-I 〃
〃
〃54 2-CF3 〃
〃
〃55 3-CF3H
3,5-di-CH3 3,5-
di-CH3 56 2-Cl 〃
〃 〃5
7 3-Cl 〃
〃 〃58
2-CN〃
〃 〃59
3-CN〃
〃 〃60
3-F 〃
2,4-di-CH3 2,4-di-C
H361 4-F 〃
〃
〃62 2-Br 〃
〃
〃63 4-Br 〃
〃 〃
64 4-I 〃
〃 〃
65 2-CF3 〃
〃 〃6
6 4-CF3 〃
〃 〃67
2-Cl 〃
〃 〃68
3-Cl 〃
〃 〃69
2-CN〃
〃 〃70
2-F 〃
2,3-di-CH3 2,3-di-CH
371 4-F 〃
〃
〃72 4-Br 〃
〃 〃
73 4-I 〃
〃 〃
74 4-CF3 〃
〃 〃7
5 2-Cl 〃
〃 〃76
4-F 〃
3,4-di-CH3 3,4-di
-CH377 4-Br 〃
〃
〃78 4-I 〃
〃
〃79 4-CF3 〃
〃
〃80 2-Cl 〃
〃
〃81 2-CN 〃
〃 〃
82 2-F 〃
4-Cl4
-Cl 83 4-F
〃 〃
〃84 4-Br H
4-Cl
4-Cl 85 3-I
〃 〃
〃86 3-CF3
〃 〃
〃87 4-CF3
〃 〃
〃88 2-Cl
〃 〃
〃89 2-CN 〃
〃
〃90 4-F 〃
4-Br
4-Br 91 4-Br
〃 〃
〃92 4-CF3
〃 〃
〃93 2-Cl
〃 〃
〃94 2-CN 〃
〃
〃95 4-F 〃
4-F
4-F96 4-Br
〃 〃
〃97 4-I
〃 〃
〃98 4-CF3 〃
〃
〃99 2-Cl 〃
〃
〃100 2-CN 〃
〃
〃101 4-F 〃
4-I 4-
I102 4-Br 〃
〃 〃
103 4-CF3 〃
〃 〃1
04 2-CN 〃
〃 〃10
5 4-F 〃
4-C2H5 4-C2
H5106 3-Br 〃
〃
〃107 4-Br 〃
〃 〃
108 4-CF3 〃
〃 〃1
09 2-Cl〃
〃 〃11
0 2-CN 〃
〃 〃111
3-F 〃
4-n-C3H7 4-n-C3
H7 112 4-F 〃
〃
〃113 4-Br H
4-n-C3H7 4
-n-C3H7 114 2-CF3
〃 〃
〃115 3-Cl
〃 〃
〃116 2-CN
〃 〃
〃117 2-F
〃 4-iso-C3H7
4-iso-C3H7 118 2-Br
〃 〃
〃119 4-Br
〃 〃
〃120 4-Br
〃 4-t-C4-H9
4-t-C4-H9121 2
-Cl 〃 〃
〃123 3-
CN 〃 〃
〃124 4-B
r〃4-OC2
H5 4-OC2H5 125
2-CN〃
〃 〃126
4-Br 〃 4-
t-OC4H9 4-t-OC4H912
7 4-Br 〃
4-CN 4-CN
128 4-F 〃
〃
〃129 4-CF3 〃
〃 〃
130 2-Cl 〃
〃 〃1
31 2-CN 〃
〃 〃13
2 4-CF3 〃
4-CF3 4-CF3
133 2-CN〃
〃 〃
134 4-Br 〃
〃 〃1
35 4-Br 〃
4-N(C2H5)2 4-N(C
2H5) 2 136 3-F
〃 〃
〃137 2-Cl
〃 〃
〃138 4-Br
〃 4-N(CH3)2
4-N(CH3)2 139 4-Br
〃 4-N(CH2-P
h)24-N(CH2-Ph)2140
3-Br 〃
4-CH3 H141
4-Br 〃
〃 〃142
4-CF3 〃
〃 〃143
3-CNH2-
CH3 H144
4-Br 〃 3-
CH3〃145
2-Cl 〃 4-
OCH3〃146
4-Br 〃 4-
CH3 4-OCH3147
2-Cl 〃
〃 2-Cl 148
2-F 4-F
H H149
2-Cl 4,6-di-Cl
〃 〃150
2-Br 4,5-di-Br
〃 〃151
2-Cl 3-Cl
〃 〃152
4-CN 2-CN
〃 〃153
4-Cl 2-CH3
〃 〃154
2-Cl 4-CH3
〃 〃155
2-Br 〃
〃 〃156
2-Cl 5-CH3
〃 〃157
2-F 3,4,5,6-F
〃 〃158
3-Cl 5-Cl
〃 〃159
2-Cl 3-CH3, 4-Cl
〃 〃160
2-Br 4-C2H5
〃 〃161
2-Cl 4-iso-C3H7
〃 〃162
2-Cl 4-Cl
2,4-di-Cl 2,4-di
-Cl163 2-Cl4-C
H3 4-OCH3
4-OCH3164 3-Cl
〃 4-CH3
4-CH3 165 2-Br
〃 4-OCH3
4-OCH3166 2-Cl
4-Cl 4-Cl
H167 2-C
l 4-CH3 4-CH
3 〃168 2-
Br〃4-OC
H3 〃169 2-
Cl4-Cl4-
Cl4-Br 170
2-Cl 4-CH3
4-CH3 4-CH317
1 2-F H
2-CH3 2-C
H3172 3-Br H
2-CH3
2-CH3 173 4-Br 〃
〃 〃1
74 3-CF3 〃
〃 〃17
5 3-Cl 〃
〃 〃176
2-CN〃
〃 〃177
2-F 〃
3-CH3 3-CH3
178 4-Br 〃
〃 〃1
79 2-CF3 〃
〃 〃18
0 2-Cl 〃
〃 〃181
3-CN〃
〃 〃182
2-F 〃
2-OCH3 2-OCH3
183 3-F 〃
〃 〃
184 2-Br 〃
〃 〃1
85 4-Br 〃
〃 〃18
6 2-Cl 〃
〃 〃187
4-F 〃
3-OCH3 3-OCH
3188 4-Br 〃
〃 〃
189 3-ClH
〃 〃1
90 2-CN〃
〃 〃19
1 2-Cl 4-Cl
3-iso-C3H7 3-iso
-C3H7 192 2-I
3-CH3 2-C2H5
H193 2-CN
4-CH3 3-C2H5
3-C2H5194 2-F
3,4,5,6-tetra-F 4-tert-
C4H9 4-tert-C4H9 195
2-Cl 3,4,5,6-tetra-C
l 4-C2H5 4-C2H5 [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] [Chemical formula 10] [Chemical formula 10] [Chemical formula 11] [Chemical formula 12] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical 20] [Chemical 21] [Chemical 21] [Chemical 22] [Chemical 23]

[Brief explanation of the drawing]

FIG. 1 is a sectional view of an example of an electrophotographic photoreceptor according to the present invention.

FIG. 2 is a sectional view of another example of an electrophotographic photoreceptor according to the present invention.

FIG. 3 is a sectional view of another example of an electrophotographic photoreceptor according to the present invention.

FIG. 4 is a sectional view of another example of an electrophotographic photoreceptor according to the present invention.

FIG. 5 is a sectional view of another example of an electrophotographic photoreceptor according to the present invention.

FIG. 6 is a sectional view of still another example of an electrophotographic photoreceptor according to the present invention.

[Explanation of symbols]

1 Support 2 Carrier generation layer 3 Carrier transport layer 5 Intermediate layer 6 Layer containing a carrier generation substance and a carrier transport substance

Claims (1)

[Claims] 1. An electrophotographic photoreceptor containing a bisstyryl compound represented by the following general formula [I]. [Formula 1] [However, when n≧0 and n=0, R1 is a chlorine atom or a cyano group substituted at the 2- or 3-position with respect to the substituted amino group, or 2-, 3
- or a fluorine atom substituted at the 4- position,
It is a functional group selected from a bromine atom, an iodine atom, and a halogenated alkyl group having 1 to 4 carbon atoms. When n≧1, R1 is a halogen atom, a cyano group, or a halogenated alkyl group having 1 to 4 carbon atoms, which is substituted at the 2-, 3- or 4-position with respect to the substituted amino group. R
2 is a functional group selected from a lower alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, and a halogenated alkyl group having 1 to 4 carbon atoms. The two Cys may be different and are a heterocyclic group or a heterocyclic group fused with a benzene ring. {However, q≧0 and r≧0. two R3, R4
may be different from each other, lower alkyl group having 1 to 4 carbon atoms, lower alkoxy group having 1 to 4 carbon atoms, halogen atom, cyano group, halogenated alkyl group having 1 to 4 carbon atoms, carbon atom It is a functional group selected from dialkylamino groups and dialkyl groups of numbers 1 to 4. }]