JPH0115056B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing a pyrarizoline compound suitable as a charge transport material in a photosensitive layer having a charge generation layer and a charge transport layer. Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide, and zinc oxide are known as photoconductive materials used in electrophotographic photoreceptors. These photoconductive materials have a number of advantages, such as being able to be charged to an appropriate potential in the dark, having little charge dissipation in the dark, or quickly dissipating the charge when irradiated with light. However, it also has various drawbacks. For example, selenium-based photoreceptors easily crystallize due to factors such as temperature, humidity, dust, and pressure. Especially when the ambient temperature exceeds 40°C, crystallization becomes significant, resulting in decreased charging performance and white spots on images. There is a drawback when this occurs. Furthermore, selenium-based photoreceptors and cadmium sulfide photoreceptors have the disadvantage that stable durability cannot be obtained when used over time under high humidity. In addition, zinc oxide photoreceptors require the sensitizing effect of sensitizing dyes such as rose bengal, but such sensitizing dyes cause charge deterioration due to corona charging and photobleaching due to exposure light, so it may take a long time. It has the disadvantage that it cannot provide a stable image over a long period of time. On the other hand, various organic photoconductive polymers including polyvinylcarbazole have been proposed, but these polymers are superior in terms of film formability and lightness compared to the inorganic photoconductive materials mentioned above. Nevertheless, it has been difficult to put them into practical use until now because they are inferior to inorganic photoconductive materials in terms of sensitivity and durability. For these reasons, a laminated structure in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been proposed in recent years. Electrophotographic photoreceptors using this laminated structure as a photosensitive layer can now be improved in terms of sensitivity to visible light, charge retention, surface strength, and the like. Such electrophotographic photoreceptors are disclosed, for example, in JP-A-49-105537, JP-A-51-90827, US Pat. No. 3,484,237, and US Pat. No. 3,871,882. However, even with such an electrophotographic photoreceptor, it is still not possible to obtain a sufficiently satisfactory sensitivity, and moreover, the surface potential changes when repeatedly charged and exposed, especially when repeatedly exposed and charged. There are disadvantages such as an increase in bright area potential and a decrease in dark area potential. SUMMARY OF THE INVENTION An object of the present invention is to provide a new electrophotographic photoreceptor that can eliminate the above-mentioned drawbacks or disadvantages. Another object of the invention is to provide new organic photoconductive materials. Another object of the present invention is to provide a novel pyrazoline compound suitable for use as a charge transport material in a photosensitive layer having the aforementioned laminated structure. Another object of the present invention is to provide a photosensitive layer having a charge transport layer and a charge generation layer containing a novel charge transport material. Another object of the present invention is to provide an electrophotographic photoreceptor with improved sensitivity and durability. The present invention is characterized by an electrophotographic photoreceptor having a layer containing a compound represented by the following general formula []. General formula [] In the formula, etc.), and these heterocyclic groups are alkyl groups (e.g. methyl, ethyl, propyl, iso
-propyl group, butyl group, t-butyl group, etc.) or an alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.) as a substituent. R ₁ represents an aryl group such as a phenyl group, a naphthyl group or an anthralyl group. These aryl groups are particularly di-alkyl-substituted amino groups (e.g. N,N-dimethylamino, N,N-
Diethylamino group, N,N-dipropylamino group, N,N-dibutylamino group, N,N-dipentylamino group, N-methyl-N-ethylamino group, N-methyl-N-propylamino group, N- ethyl-N-propylamino group, etc.), cyclic amino groups (e.g., morpholino group, piperazino group, pyrrolidino group, etc.), and alkoxy groups (e.g., methoxy group, ethoxy group, propyloxy group, butoxy group, etc.). It is preferable that In addition, the alkyl group and alkoxy group of the above-mentioned dialkyl-substituted amino group may be an appropriate atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.) or an organic residue (e.g.,
tolyl group, xylyl group, chlorophenyl group, phenyl group, naphthyl group, hydroxy group, carboxy group, cyano group, amino group, etc.). Typical R ₁ is 4-N,
N-dimethylaminophenyl group, 4-N,N-diethylaminophenyl group, 4-N,N-dipropylaminophenyl group, 4-N,N-dibutylaminophenyl group, 4-N,N- dibenzylaminophenyl group, 4-monomorinophenyl group, 4-piperidinophenyl group, 4-pyrrolidinophenyl group,
Examples include dialkyl-substituted aminophenyl groups such as 4-methoxyphenyl group, 4-ethoxyphenyl group, and 4-butoxyphenyl group, di-aralkyl-substituted aminophenyl group, cyclic aminophenyl group, and alkoxyphenyl group. R ₂ and R ₃ represent a hydrogen atom or an aryl group. Aryl groups are particularly di-alkyl-substituted amino groups (e.g. N,N-dimethylamino, N,
N-diethylamino group, N,N-dipropylamino group, N,N-dibutylamino group, N,N-dipentylamino group, N-methyl-N-ethylamino group, N-methyl-N-propylamino group, N-ethyl-N-propylamino group, etc.), cyclic amino groups (e.g., morpholino group, piperazino group, pyrrolidino group, etc.) and alkoxy groups (e.g., methoxy group, ethoxy group, propyloxy group, butoxy group, etc.). It is preferable to have. In addition, the alkyl group and alkoxy group of the above-mentioned dialkyl-substituted amino group may be an appropriate atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.) or an organic residue (e.g.,
tolyl group, xylyl group, chlorophenyl group, phenyl group, naphthyl group, hydroxy group, carboxy group, cyano group, amino group, etc.). However, R ₂ and R ₃ are never hydrogen atoms at the same time. Typical _R2 and _R3
Examples include 4-N,N-dimethylaminophenyl group, 4-N,N-diethylaminophenyl group, 4
-N,N-dipropylaminophenyl group, 4-
N,N-dipropylaminophenyl group, 4-N,
N-dibutylaminophenyl group, 4-N,N-dibenzylaminophenyl group, 4-mormolinophenyl group, 4-piperidinophenyl group, 4-pyrrolidinophenyl group, 4-methoxyphenyl group , 4-
Examples include di-alkyl-substituted aminophenyl groups such as ethoxyphenyl group and 4-butoxyphenyl group, di-aralkyl-substituted aminophenyl group, cyclic aminophenyl group, and alkoxyphenyl group. R ₄ and R ₅ are hydrogen atoms or optionally substituted alkyl groups (e.g., methyl group, ethyl group,
Propyl group, iso-propyl group, butyl group, t-
Alkyl groups having 1 to 5 carbon atoms such as butyl group, amyl group, t-amyl group, or benzyl group, chlorobenzyl group, dichlorobenzyl group, trichlorobenzyl group, bromobenzyl group, methylbenzyl group, dimethylbenzyl group, cyano benzyl group,
2-phenylethyl group, α-naphthylmethyl group,
β-naphthylmethyl group, vinylmethyl group, 2-chloroethyl group, 3-chloropropyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2
-methoxyethyl group, 3-methoxypropyl group,
4-methoxybutyl group, 2-phenoxyethyl group) or aryl group (e.g., phenyl group, tolyl group, xylyl group, biphenyl group, ethyl phenyl group, diethylphenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group) enyl group, carboxyphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl group, dibromophenyl group, aminophenyl group, N,N-dimethylaminophenyl group, N,N-diethylaminophenyl group , N,N-dibenzylaminophenyl group, α-
naphthyl group, β-naphthyl group, etc.). However, R ₄ and R ₅ are never hydrogen atoms at the same time.
Further, n is 0 or 1. Representative examples of the pyrazoline compound represented by the general formula [] are as follows. Pyrazoline compound (1) 1-[pyridyl-(3)]-3-(4-N,N-dimethylaminostyryl)-4-methyl-5-(4
-N,N-dimethylaminophenyl)pyrazoline (2) 1-[pyridyl-(3)]-3-(4-N,N-diethylaminostyryl)-4-methyl-5-(4
-N,N-diethylaminophenyl)pyrazoline (3) 1-[pyridyl-(3)]-3-(4-N,N-dibenzylaminostyryl)-4-methyl-5-
(4-N,N-dibenzylaminophenyl)pyrazoline (4) 1-[pyridyl-(3)]-3-(4-N-ethyl-N-propylaminostyryl)-4-methyl-5-( 4-N-ethyl-N-propylaminophenyl)pyrazoline (5) 1-[pyridyl-(3)]-3-(4-N,N-diethylaminostyryl)-4-methyl-5-(4
-N,N-dibenzylaminophenyl)pyrazoline (6) 1-[pyridyl-(3)]-3-(4-morpholinostyryl)-4-methyl-5-(4-morpholinophenyl)pyrazoline (7 ) 1-[pyridyl-(3)]-3-(4-piperidinostyryl)-4-methyl-5-(4-piperidinophenyl)pyrazoline(8) 1-[pyridyl-(3)]- 3-(4-pyrrolidinostyryl)-4-methyl-5'-(4-pyrrolidinophenyl)pyrazoline (9) 1-[pyridyl-(3)]-3-(4-methoxystyryl)-4- Methyl-5-(4-methoxyphenyl)pyrazoline (10) 1-[pyridyl-(3)]-3-(4-ethoxystyryl)-4-methyl-5-(4-ethoxyphenyl)pyrazoline (11 ) 1-[pyridyl-(3)]-3-(4-N,N-diethylaminostyryl)-4-methyl-5-(4
-methoxyphenyl)pyrazoline (12) 1-[pyridyl-(3)]-4-methyl-5,5-
Diphenyl-3-(4-N,N-diethylaminostyryl)pyrazoline (13) 1-[pyridyl-(3)]-4-methyl-3,5
-di-(4-N,N-diethylaminophenyl)
Pyrazoline (14) 1-[pyridyl-(3)]-4-methyl-3,5
-di-(4-N,N-dibenzylaminophenyl)pyrazoline (15) 1-[pyridyl-(3)]-4-methyl-3,5
-di-(4-morpholinophenyl)pyrazoline (16) 1-[pyridyl-(3)]-3-(4-N,N-
dimethylaminostyryl)-4-ethyl-5-
(4-N,N-dimethylaminophenyl)pyrazoline (17) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-ethyl-5-
(4-N,N-diethylaminophenyl)pyrazoline (18) 1-[pyridyl-(3)]-3-(4-N,N-
dibenzylaminostyryl)-4-ethyl-5
-(4-N,N-dibenzylaminophenyl)
Pyrazoline (19) 1-[pyridyl-(3)]-3-(4-N-ethyl-N-propylaminostyryl)-4-ethyl-5-(4-N-ethyl-N-propylaminophenyl) Pyrazoline (20) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-ethyl-5-
(4-N,N-dibenzylaminophenyl)pyrazoline (21) 1-[pyridyl-(3)]-3-(4-morpholinostyryl)-4-ethyl-5-(4-morpholinophenyl)pyrazoline (22) 1-[pyridyl-(3)]-3-(4-piperidinostyryl)-4-ethyl-5-(4-piperidinophenyl)pyrazoline(23) 1-[pyridyl-(3) ]-3-(4-pyrrolidinostyryl)-4-ethyl-5-(4-pyrrolidinophenyl)pyrazoline (24) 1-[pyridyl-(3)]-3-(4-methoxystyryl)-4 -Ethyl-5-(4-methoxyphenyl)pyrazoline (25) 1-[pyridyl-(3)]-3-(4-ethoxystyryl)-4-ethyl-5-(4-ethoxyphenyl)pyrazoline ( 26) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-ethyl-5-
(4-methoxyphenyl)pyrazoline (27) 1-[pyridyl-(3)]-4-ethyl-5,5
-diphenyl-3-(4-N,N-diethylaminostyryl)pyrazoline (28) 1-[pyridyl-(3)]-4-ethyl-3,5
-di-(4-N,N-diethylaminophenyl)
Pyrazoline (29) 1-[pyridyl-(3)]-4-ethyl-3,5
-di-(4-N,N-dibenzylaminophenyl)pyrazoline (30) 1-[pyridyl-(3)]-4-ethyl-3,5
-di-(4-morpholinophenyl)pyrazoline (31) 1-[pyridyl-(3)]-3-(4-N,N-
dimethylaminostyryl)-4-benzyl-5
-(4-N,N-dimethylaminophenyl)pyrazoline (32) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-benzyl-5
-(4-N,N-diethylaminophenyl)pyrazoline (33) 1-[pyridyl-(3)]-3-(4-N,N-
dibenzylaminostyryl)-4-benzyl-
5-(4-N,N-dibenzylaminophenyl)
Pyrazoline (34) 1-[pyridyl-(3)]-3-(4-N-ethyl-N-propylaminostyryl)-4-benzyl-5-(4-N-ethyl-N-propylaminophenyl) Pyrazoline (35) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-benzyl-5
-(4-N,N-dibenzylaminophenyl)
Pyrazoline (36) 1-[pyridyl-(3)]-3-(4-morpholinostyryl)-4-benzyl-5-(4-morpholinophenyl)pyrazoline (37) 1-[pyridyl-(3)]- 3-(4-piperidinostyryl)-4-benzyl-5-(4-piperidinophenyl)pyrazoline (38) 1-[pyridyl-(3)]-3-(4-pyrrolidinostyryl)-4 -Benzyl-5-(pyrrolidinophenyl)pyrazoline (39) 1-[pyridyl-(3)]-3-(4-methoxystyryl)-4-benzyl-5-(4-methoxyphenyl)pyrazoline (40 ) 1-[pyridyl-(3)]-3-(4-ethoxystyryl)-4-benzyl-5-(4-ethoxyphenyl)pyrazoline (41) 1-[pyridyl-(3)]-3-( 4-N,N-
diethylaminostyryl)-4-benzyl-5
-(4-methoxyphenyl)pyrazoline(42) 1-[pyridyl-(3)]-4-benzyl-5,
5-diphenyl-3-(4-N,N-diethylaminostyryl)pyrazoline (43) 1-[pyridyl-(3)]-4-benzyl-3,
5-di-(4-N,N-diethylaminophenyl)pyrazoline (44) 1-[pyridyl-(3)]-4-benzyl-3,
5-di-(4-N,N-dibenzylaminophenyl)pyrazoline (45) 1-[pyridyl-(3)]-4-benzyl-3,
5-di-(4-morpholinophenyl)pyrazoline (46) 1-[pyridyl-(3)]-3-(4-N,N-
dimethylaminostyryl)-4-phenyl-5
-(4-N,N-dimethylaminophenyl)pyrazoline (47) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-phenyl-5
-(4-N,N-diethylaminophenyl)pyrazoline (48) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-(4-methylphenyl)-5-(4-N,N-dibenzylaminophenyl)pyrazoline (49) 1-[pyridyl-(3)]-3-(4-N,N-
diethylaminostyryl)-4-(3-methoxyphenyl)-5-(4-N,N-dibenzylaminophenyl)pyrazoline (50) 1-[pyridyl-(3)]-3-(4-morpholinostyryl) )-4-phenyl-5-(4-morpholinophenyl)pyrazoline (51) 1-[pyridyl-(3)]-3-(4-piperidinostyryl)-4-phenyl-5-(4-pyridyl-(3)) Peridinophenyl)pyrazoline (52) 1-[pyridyl-(3)]-3-(4-pyrrolidinostyryl)-4-phenyl-5-(4-pyrrolidinophenyl)pyrazoline (53) 1-[6 -methoxy-pyridyl-(2)]-3-
(4-N,N-dimethylaminostyryl)-4-
Methyl-5-(4-N,N-dimethylaminophenyl)pyrazoline (54) 1-[6-methoxy-pyridyl-(2)]-3-
(4-N,N-diethylaminostyryl)-4-
Methyl-5-(4-N,N-diethylaminophenyl)pyrazoline (55) 1-[6-methoxy-pyridyl-(2)]-3-
(4-N,N-dibenzylaminostyryl)-4
-Ethyl-5-(4-N,N-dibenzylaminophenyl)pyrazoline (56) 1-[6-methoxy-pyridyl-(2)]-3-
(4-N-ethyl-N-propylaminostyryl)-4-phenyl-5-(4-N-ethyl-N
-propylaminophenyl)pyrazoline (57) 1-[6-methoxy-pyridyl-(2)]-3-
(4-N,N-diethylaminostyryl)-4-
Benzyl-5-(4-N,N-dibenzylaminophenyl)pyrazoline (58) 1-[6-methoxy-pyridyl-(2)]-3-
(4-morpholinostyryl)-4-methyl-5-
(4-morpholinophenyl)pyrazoline (59) 1-[6-methoxy-pyridyl-(2)]-3-
(4-piperidinostyryl)-4-methyl-5-
(4-piperidinophenyl)pyrazoline (60) 1-[6-methoxy-pyridyl-(2)]-3-
(4-pyrrolidinostyryl)-4-methyl-5-
(4-pyrrolidinophenyl)pyrazoline (61) 1-[6-methoxy-pyridyl-(2)]-3-
(4-methoxystyryl)-4-methyl-5-
(4-methoxyphenyl)pyrazoline (62) 1-[6-methoxy-pyridyl-(2)]-3-
(4-ethoxystyryl)-4-methyl-5-
(4-Ethoxyphenyl)pyrazoline (63) 1-[6-methoxy-pyridyl-(2)]-3-
(4-N,N-diethylaminostyryl)-4-
Methyl-5-(4-methoxyphenyl)pyrazoline (64) 1-[quinolyl-(2)]-3-(4-N,N-
dimethylaminostyryl)-4-methyl-5-
(4-N,N-dimethylaminophenyl)pyrazoline (65) 1-[quinolyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-diethylaminophenyl)pyrazoline (66) 1-[quinolyl-(2)]-3-(4-N,N-
dibenzylaminostyryl)-4-ethyl-5
-(4-N,N-dibenzylaminophenyl)
Pyrazoline (67) 1-[quinolyl-(2)]-3-(4-N-ethyl-N-propylaminostyryl)-4-methyl-5-(4-N-ethyl-N-propylaminophenyl) Pyrazoline (68) 1-[quinolyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-dibenzylaminophenyl)pyrazoline (69) 1-[quinolyl-(2)]-3-(4-morpholinostyryl)-4-methyl-5-(4-morpholinophenyl)pyrazoline (70) 1-[quinolyl-(2)]-3-(4-piperidinostyryl)-4-methyl-5-(4-piperidinophenyl)pyrazoline(71) 1-[quinolyl-(2) ]-3-(4-pyrrolidinostyryl)-4-methyl-5-(4-pyrrolidinophenyl)pyrazoline (72) 1-[quinolyl-(2)]-3-(4-methoxystyryl)-4 -Methyl-5-(4-methoxyphenyl)pyrazoline (73) 1-[quinolyl-(2)]-3-(4-ethoxystyryl)-4-methyl-5-(4-ethoxyphenyl)pyrazoline ( 74) 1-[quinolyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-methoxyphenyl)pyrazoline (75) 1-[lepidyl-(2)]-3-(4-N,N-
dimethylaminostyryl)-4-methyl-5-
(4-N,N-dimethylaminophenyl)pyrazoline (76) 1-[Lepidyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-diethylaminophenyl)pyrazoline (77) 1-[lepidyl-(2)]-3-(4-N,N-
dibenzylaminostyryl)-4-propyl-
5-(4-N,N-dibenzylaminophenyl)
Pyrazoline (78) 1-[lepidyl-(2)]-3-(4-N-ethyl-N-propylaminostyryl)-4-(4-
methylbenzyl)-5-(4-N-ethyl-N-
propylaminophenyl)pyrazoline (79) 1-[lepidyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-dibenzylaminophenyl)pyrazoline (80) 1-[lepidyl-(2)]-3-(4-morpholinostyryl)-4-methyl-5-(4-morpholinophenyl)pyrazoline (81) 1-[Lepidil-(2)]-3-(4-piperidinostyryl)-4-methyl-5-(4-piperidinophenyl)pyrazoline(82) 1-[Lepidil-(2) ]-3-(4-pyrrolidinostyryl)-4-methyl-5-(4-pyrrolidinophenyl)pyrazoline (83) 1-[lepidyl-(2)]-3-(4-methoxystyryl)-4 -Methyl-5-(4-methoxyphenyl)pyrazoline (84) 1-[lepidyl-(2)]-3-(4-ethoxystyryl)-4-methyl-5-(4-ethoxyphenyl)pyrazoline ( 85) 1-[Lepidil-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-methoxyphenyl)pyrazoline (86) 1-[pyridyl-(2)]-3-(4-N,N-
dimethylaminostyryl)-4-methyl-5-
(4-N,N-dimethylaminophenyl)pyrazoline (87) 1-[pyridyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-diethylaminophenyl)pyrazoline (88) 1-[pyridyl-(2)]-3-(4-N,N-
dibenzylaminostyryl)-4-methyl-5
-(4-N,N-dibenzylaminophenyl)
Pyrazoline (89) 1-[pyridyl-(2)]-3-(4-N-ethyl-N-propylaminostyryl)-4-methyl-5-(4-N-ethyl-N-propylaminophenyl) Pyrazoline (90) 1-[pyridyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-N,N-dibenzylaminophenyl)pyrazoline (91) 1-[pyridyl-(2)]-3-(4-morpholinostyryl)-4-methyl-5-(4-morpholinophenyl)pyrazoline (92) 1-[pyridyl-(2)]-3-(4-piperidinostyryl)-4-methyl-5-(4-piperidinophenyl)pyrazoline(93) 1-[pyridyl-(2) ]-3-(4-pyrrolidinostyryl)-4-methyl-5-(4-pyrrolidinophenyl)pyrazoline (94) 1-[pyridyl-(2)]-3-(4-methoxystyryl)-4 -Methyl-5-(4-methoxyphenyl)pyrazoline (95) 1-[pyridyl-(2)]-3-(4-ethoxystyryl)-4-methyl-5-(4-ethoxyphenyl)pyrazoline ( 96) 1-[pyridyl-(2)]-3-(4-N,N-
diethylaminostyryl)-4-methyl-5-
(4-methoxyphenyl)pyrazoline (97) 1-[carbazolyl-(3)]-3-(4-N,
N-dimethylaminostyryl)-4-methyl-
5-(4-N,N-dimethylaminophenyl)
Pyrazoline (98) 1-[carbazolyl-(3)]-3-(4-N,
N-diethylaminostyryl)-4-methyl-
5-(4-N,N-diethylaminophenyl)
Pyrazoline (99) 1-[carbazolyl-(3)]-3-(4-N,
N-diethylaminostyryl)-4-phenyl-5-(4-N,N-diethylaminophenyl)
Pyrazoline (100) 1-[9-ethyl-carbazolyl-(3)]-
3-(4-N,N-diethylaminostyryl)-
4-Methyl-5-(4-N,N-diethylaminophenyl)pyrazoline (101) 1-[9-ethyl-carbazolyl-(3)]-
3-(4-N,N-diethylaminostyryl)-
4-Benzyl-5-(4-N,N-diethylaminophenyl)pyrazoline (102) 1-[pyridyl-(3)]-3-(α-methyl-4-N,N-diethylaminostyryl)-5
-(4-N,N-diethylaminophenyl)pyrazoline (103) 1-[pyridyl-(3)]-3-(α-methyl-4-N,N-diethylaminostyryl)-4
-Methyl-5-(4-N,N-diethylaminophenyl)pyrazoline (104) 1-[lepidyl-(2)]-3-(α-benzyl-4-N,N-diethylaminostyryl)-
4-Methyl-5-(4-N,N-diethylaminophenyl)pyrazoline Representative examples of these pyrazoline compounds are summarized in a table below.

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[Table] These compounds can be synthesized using known synthesis methods, such as refluxing an unsaturated ketone represented by the following general formula (a) and a hydrazino compound represented by the general formula (b) in alcohol with a small amount of acetic acid for several hours. easily obtained by General formula (a) (b) X-NH- _NH2 (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and The above can be used in combination. A preferred embodiment of the electrophotographic photoreceptor of the present invention uses a photosensitive layer having a laminated structure of a charge transport layer containing the above-mentioned pyrazoline compound as a charge transport substance and a charge generation layer described below. The charge transport layer is formed by applying a solution in which the above-mentioned pyrazoline compound and binder are dissolved in a suitable solvent.
Preferably, it is formed by drying. Examples of the binder used here include polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenol resin, epoxy resin, polyester resin, polysulfone, alkyd resin, polycarbonate, polyurethane, or a combination of these resins. Examples include copolymer resins containing two or more repeating units, with polyester resins and polycarbonates being particularly preferred. Additionally, photoconductive polymers that themselves have charge transport capabilities, such as poly-N-vinylcarbazole, can also be used as binders. The blending ratio of this binder and charge transport compound is
Preferably, the charge transport compound is contained in an amount of 10 to 500 parts by weight per 100 parts by weight of the binder. The thickness of this charge transport layer is between 2 and 100 microns, preferably between 5 and 30 microns. Further, the solvent used in forming the charge transport layer of the present invention includes many useful organic solvents. Typical examples include aromatic hydrocarbons such as benzene, naphthalene, toluene, xylene, mesitylene, and chlorobenzene;
Ketones such as acetone and 2-butanone, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and ethylene chloride, cyclic or linear ethers such as tetrahydrofuran and ethyl ether, or mixed solvents thereof. can be mentioned. The charge transport layer of the present invention can contain various additives. Such additives include diphenyl, diphenyl chloride, O-terphenyl,
P-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, dilaurylthiopropionate, 3,5-dinitrosalicylic acid,
Examples include various fluorocarbons and silicone oil. As the charge generation substance used in the charge generation layer, any material can be used as long as it absorbs light and generates charge carriers with extremely high efficiency. Preferred materials include selenium, selenium, etc.
Inorganic materials such as tellurium, selenium/arsenic cadmium sulfide, amorphous silicon, pyrylium dyes,
Thiopyrylium dyes, triarylmethane dyes, thiazine dyes, cyanine dyes, phthalocyanine pigments, perylene pigments, indico pigments, thioindico pigments, quinacridone pigments,
Examples include organic substances such as squaric acid pigments, azo pigments, and polycyclic quinone pigments. The thickness of the charge generation layer is preferably 5 microns or less, preferably 0.05 to 3 microns. The charge generation layer is provided by means such as vacuum deposition, sputtering, glow discharge or coating depending on the type of charge generation material used. When coating, the charge-generating material is used as a binder.
There are cases where it is provided free, cases where it is provided as a resin dispersion, and cases where it is provided as a homogeneous solution of a binder and a charge generating material. When the charge generation layer is formed by applying a resin dispersion or solution of the charge generation material, the ratio of the binder in the charge generation layer should be 80% or less, preferably 40%, since a large amount of binder will affect the sensitivity.
% or less is desirable. Binders used in the charge generation layer include polyvinyl butyral, polymethyl methacrylate,
Polyester, polyvinylidene chloride, chlorinated rubber,
Polyvinyltoluene, styrene-maleic anhydride copolymer, polystyrene, polyvinyl chloride, emethycellulose, polyamide, polyvinylpyridine, styrene-butadiene copolymer, etc. can be used. Preferred charge generating substances in the present invention include, for example, JP-A No. 47-18545, JP-A No. 47-30328, JP-A No. 48-1988.
No. 724, No. 48-725, No. 50-1122, No. 50-1123
No. 50-38543, No. 51-23738, No. 51-
No.95852, No.51-108847, No.51-109841, No.95852, No.51-108847, No.51-109841, No.
No. 51-117637, No. 51-129234, No. 52-104131
No. 52-130331, No. 52-135736, No. 52-
No. 141229, No. 52-143827, No. 53-9537, No. 53
−9536, No. 53-37423, No. 53-37424, No. 53
−37425, No. 53-40529, No. 52-104131, No.
No. 52-130331, No. 52-135736, No. 52-141229
No. 49-11136, No. 53-46735, No. 53-
No. 58240, No. 53-64040, No. 53-74430, No. 53
−83774, No. 53-83745, No. 53-95029, No.
No. 54-29645, No. 54-37748, No. 54-85032,
No. 52-47824, No. 53-133037, No. 53-37422
No. 53-44028, No. 53-89433, No. 53-
No. 89434, No. 54-17732, No. 55-60958, No. 55
Phthalocyanine pigments disclosed in JP-A-59468 and JP-A-55-149634, JP-A-47-37543 and JP-A-48
-43942, 48-70538, 49-91648, same
No. 52-4241, No. 52-8832, No. 52-55643, No. 52-55643, No.
No. 53-95033, No. 53-132347, No. 53-133445,
No. 54-12742, No. 54-2129, No. 54-2738,
No. 54-17733, No. 54-17734, No. 54-17735,
No. 54-20736, No. 54-20737, No. 54-21728,
No. 54-22834, No. 54-79632, No. 54-94836,
No. 54-109438, No. 54-111352, No. 54-119926
No. 54-119927, No. 54-145142, No. 55-
No. 33112, No. 55-33113, No. 55-67751, No. 55
-69147, 55-69148, 55-117151, same
No. 56-1944, No. 56-2352, No. 56-2353, No. 56
-5553, 56-9752, 56-9753, 56-
Publications No. 21128, No. 56-22438, No. 56-32146,
Patent Application No. 55-18574, No. 55-18575, No. 55-
No. 21670, No. 55-72752, No. 55-124501, No. 55
−124502, No. 55-137708, No. 55-138263,
No. 55-138264, No. 55-138265, No. 55-138266
No. 55-153814, No. 55-166557, No. 56-
Monoazo pigments, bisazo pigments, trisazo pigments disclosed in the specifications of No. 44066 and No. 55-132965, etc.
JP-A-49-105536, JP-A No. 52-55643, JP-A No. 55-
53335, etc., Sukuvarylium dyes disclosed in various publications, JP-A No. 47-30331, JP-A No. 50-61233, JP-A No. 54
- Indigo dyes disclosed in various publications such as No. 139540, JP-A No. 47-30330, JP-A No. 54-126036, JP-A No. 49-
Perylene pigments disclosed in Publications No. 128734, No. 55-36849, No. 55-65959, etc., JP-A-49-128734
Dioxane pigments disclosed in publications such as JP-A No. 1973
−Imidazole pigments disclosed in Publication No. 18543, etc.;
Thioxanthin dyes disclosed in JP-A-52-105828, etc., JP-A-47-18544, JP-A-50-23232
Examples include polycyclic quinone-based pigments disclosed in No. 1 and various publications. Some typical charge generating substances are listed below. Charge generating substances (1) Amorphous silicon (2) Selenium-tellurium (3) Selenium-arsenic sulfide cadmium (31) Copper phthalocyanine These pigments can be used alone or in combination of two or more. Further, the crystal form of these pigments may be α type, β type, or any other type, but β type is particularly preferred. The electrophotographic photoreceptor of the present invention is produced by coating a charge generation layer containing the pigment described above on a suitable support,
It can be produced by using a photosensitive layer having a structure in which a charge transport layer is laminated on the charge generation layer. This type of electrophotographic photoreceptor includes an intermediate layer provided on a suitable support, a charge generation layer containing the pigment described above formed thereon, and a charge transport layer described below formed thereon. Also good. This intermediate layer prevents the injection of free charges from the conductive support to the photosensitive layer when the photosensitive layer having a laminated structure is charged, and also serves as an adhesive that holds the photosensitive layer integrally bonded to the conductive support. It shows the action as a layer. This intermediate layer is made of metal oxide such as aluminum oxide, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, phenolic resin, epoxy resin, polyester resin, alkyd resin, polycarbonate, polyurethane, polyimide resin, vinylidene chloride resin, Vinyl chloride-vinyl acetate copolymer, casein, gelatin, polyvinyl alcohol, water-soluble polyethylene, nitrocellulose, etc. can be used. The thickness of this intermediate layer or adhesive layer is suitably 0.1 to 5 microns, preferably 0.5 to 3 microns. Further, a laminated structure may be used in which the charge generation layer is provided on the charge transport layer, and in this case, an appropriate surface protection layer may be formed. The charge generation layer can be provided by means such as vacuum deposition, sputtering, glow discharge or coating depending on the type of charge generation material used. When coating, the charge-generating material is used as a binder.
There are cases where it is provided free, cases where it is provided as a resin dispersion, and cases where it is provided as a homogeneous solution of a binder and a charge generating material. When dispersing pigments, known methods such as ball mills and attritors can be used to disperse pigment particles.
It is desirable that the thickness be 5 μ or less, preferably 2 μ or less, and most preferably 0.5 μ or less. The pigment can also be applied by dissolving it in an amine solvent such as ethylenediamine. Conventional methods such as blade, Mayer bar, and spray dipping are used for application. The thickness of the charge generation layer is 5μ or less, preferably 0.01 to 1μ
is desirable. Further, if necessary, the surface of the charge generation layer can be polished to a mirror finish in order to uniformly inject carriers into the charge transport layer above the charge generation layer. A charge transport layer is provided on the charge generation layer provided in this manner. If the charge transport material does not have a film-forming ability, the charge transport layer described above can be formed by applying a solution prepared by dissolving a binder in a suitable organic solvent and drying it by a conventional method. As another specific example of the electrophotographic photoreceptor of the present invention, for example, the above-mentioned pyrazoline compound is used as a charge transport material, and an insulating binder (the binder itself is a charge transport material such as poly-N-vinylcarbazole) is used. A photosensitive layer comprising a pigment such as the bisazo pigment described above dispersed in a charge transporting medium comprising: (a) may be formed on the conductive layer. Examples of the insulating binder and charge transport material used in this case include JP-B No. 52-1667, JP-A No. 47-30328, JP-A No. 47-30328,
Those disclosed in various publications such as No. 18545 can be used. The support used in the electrophotographic photoreceptor of the present invention may be any type of conductive layer conventionally used as long as it is imparted with conductivity. Specifically, metal sheets or metals such as aluminum, panadium, molybdenum, chromium, cadmium, titanium, nickel, copper, zinc, palladium, indium, tin, platinum, gold, stainless steel, and brass are vapor-deposited or laminated. Examples include plastic sheets. The electrophotographic photoreceptor of the present invention can be used not only for electrophotographic copying machines, but also for laser printers,
It can also be widely used in electrophotographic applications such as CRT printers and electrophotographic plate making systems. According to the present invention, the sensitivity is significantly higher than that of electrophotographic photoreceptors using conventional organic photoconductive materials, and moreover, repeated charging and exposure are not required.
There is no increase in bright area potential and no decrease in dark area potential even when the test is performed over 10,000 times. Hereinafter, the present invention will be explained according to examples. Example 1 An ammonia aqueous solution of defatted casein (11.2 g of casein, 1 g of 28% ammonia water, 222 g of water) was placed on an aluminum plate.
ml) with a Mayer bar and dry, coating amount 1.0
An adhesive layer of g/m ² was formed. Next, 5 g of bisazo pigment with the following structural formula and 2 g of butyral resin (butyralization degree 63 mol%) were dispersed in a ball mill for 40 hours with a solution dissolved in 95 ml of ethanol, and then coated on the adhesive layer with a Meyer bar and dried. A charge generation layer with a subsequent coating weight of 0.2 g/m ² was formed. bisazo pigment (Pigment No. 10 in the above example) Next, 1-[pyridyl-(3)]-3-(4-N,N
-diethylaminostyryl)-4-methyl-5-
(4-N,N-diethylaminophenyl)pyrazoline (the exemplified pyrazoline compound No. 2) 5 g,
A solution prepared by dissolving 5 g of poly-4,4'-dioxydiphenyl-2,2'-propane carbonate (molecular weight 30,000) in 70 ml of tetrahydrofuran is applied onto the charge generation layer and dried to form a charge with a coating weight of 10 g/ ^m2. A transport layer was formed. The electrophotographic photoreceptor prepared in this way was heated at 20°C.
After controlling the humidity at 65% (relative humidity), corona charging was performed statically at 5 KV using an electrostatic copying paper tester Model SP-428 manufactured by Kawaguchi Electric Co., Ltd., and after holding in a dark place for 10 seconds, the sample was charged at an illuminance of 5 lux. It was exposed to light and its charging characteristics were investigated. The initial voltage is Vo (-V), the potential retention rate for 10 seconds in the dark is Vk (%), and the half-decay exposure is E _1/2 (lux・sec).
The charging characteristics of this photoreceptor are shown in Table 1. Table 1 Vo: -680 volts Vk: 92% E _1/2 : 3.2 lux・sec The electrophotographic photoreceptor of this example was attached to a cylindrical cylinder, and this was used in a copying machine (manufactured by Canon Inc.).
I installed it on a modified Canon Np5500). This copier has a negative charger around the cylinder.
An exposure optical system, a developing device, and a transfer charger are arranged, and the steps are performed sequentially as the cylinder rotates to form an image on transfer paper. In the photoreceptor of this example, the bright area exposure was 15 lux・sec.
A clear image was obtained. Moreover, even when more than 25,000 copies were made using this photoreceptor, all the images obtained were of good quality. Example 2 1-[pyridyl-(3)]-3-(4-N,N-diethylaminostyryl)-4-methyl-5-(4) in the charge transport layer used in the electrophotographic photoreceptor of Example 1 −
1-[pyridyl-(3)]-3-(4-N,N
-diethylaminostyryl)-4-benzyl-5
An electrophotographic photoreceptor was prepared in exactly the same manner except that -(4-N,N-diethylaminophenyl)pyrazoline (the exemplified pyrazoline compound No. 32) was used. When the charging characteristics of this photoreceptor were measured in the same manner as in Example 1, the results shown in Table 2 were obtained. Table 2 Vo: -630 volts Vk: 92% E _1/2 : 3.0lux・sec Furthermore, the photoreceptor of this example was installed in the copying machine used in Example 1, and a similar image was formed. Clear images without fogging were obtained, and even after more than 25,000 copies were made, all the images obtained were good. Examples 3 to 27 1-[pyridyl-(3)]-3,5-di-(4-N,
Electrophotographic photoreceptors were prepared in exactly the same manner except that various pyrazoline compounds shown in Table 3 were used in place of N-diethylaminophenyl)pyrazoline. When the charging characteristics of this photoreceptor were measured in the same manner as in Example 1, the results shown in Table 3 were obtained.

【table】

[Table] The electrophotographic photoreceptors of Examples 3 to 27 were subjected to a durability test in the same manner as in Example 1, and the same results as in Example 1 were obtained. Example 28 An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that a pigment having the following structure was used in place of the bisazo pigment (No. 10) in the charge generation layer used in the electrophotographic photoreceptor of Example 1. It was created. When the charging characteristics of this photoreceptor were measured in the same manner as in Example 1, the results shown in Table 4 were obtained. Table 4 Vo: -660 volts Vk: 93% E _1/2 : 4.2 lux・sec Furthermore, the durability of this photoreceptor was measured in the same manner as in Example 1, and good images were obtained up to 25,000 sheets. was gotten. Example 29 An electrophotographic photoreceptor was prepared in the same manner as in Example 1, except that a pigment having the following structure was used in place of the bisazo pigment (No. 10) in the charge generation layer used in the electrophotographic photoreceptor of Example 1. It was created. When the charging characteristics of this photoreceptor were measured in the same manner as in Example 1, the results shown in Table 5 were obtained. Table 5 Vo: -680 volts Vk: 93% E _1/2 : 6.2 lux・sec Furthermore, the durability of this photoreceptor was measured in the same manner as in Example 1, and good images were obtained up to 25,000 sheets. was gotten. Example 30 Poly-N-vinylcarbazole (molecular weight 30000)
20g, 1-[6-methoxy-pyridyl-(2)]-3-
(4-N,N-diethylaminostyryl)-4-methyl-5-(4-N,N-diethylaminophenyl)pyrazoline (Pyrazoline compound No.
53) 3.0g polyester resin solution (Polyester Adhesive 49000 manufactured by DuPont, solid content 20%)
10g and 20g of pigment No. 4 in tetrahydrofuran.
180 ml of the mixture was charged to a ball mill and dispersed for 40 hours, and then applied onto the aluminum surface of an aluminum vapor-deposited mylar film using a Baker applicator to give a coated amount of 12 g/m ² after drying. Table 6 shows the results of charging measurement of the photoreceptor thus prepared in the same manner as in Example 1. However, the charging polarity was determined. Table 6 Vo: -470 volts Vk: 84% E _1/2 : 13.8lux・sec Example 31 A 0.2 mm thick molybdenum plate (substrate) with a cleaned surface is fixed at a predetermined position in a glow discharge deposition tank. did. Next, the inside of the tank was evacuated to a vacuum level of approximately 5×10 ⁻⁶ torr. After that, the input potential of the heater was increased to stabilize the molybdenum substrate temperature at 150°C. After that, hydrogen gas and silane gas (15% by volume relative to hydrogen gas) were introduced into the tank, and the gas flow rate and the main valve of the deposition tank were adjusted to stabilize the temperature at 0.5 torr. Next, 5MHz high-frequency power was applied to the induction coil to generate glow discharge inside the coil in the tank, resulting in an input power of 30W. An amorphous silicon film was grown on the substrate under the above conditions, and the same conditions were maintained until the film thickness reached 2 μm, after which glow discharge was discontinued. After that, turn off the heater and high frequency power supply, wait for the substrate temperature to reach 100℃, close the hydrogen gas and silane gas outflow valves, and once the inside of the tank is below 10 ^-5 torr, return to atmospheric pressure. I took out the board. Next, a charge transport layer was formed on this amorphous silicon layer in the same manner as in Example 1. The photoreceptor thus obtained was placed in a charging and exposure experimental device, charged with corona at 6 KV, and immediately irradiated with a light image. The light image was illuminated through a transmission test chart using a tungsten lamp light source. Immediately thereafter, a positively charged developer (including toner and carrier) was cascaded onto the photoreceptor surface to obtain a good toner image on the photoreceptor surface. Comparative Examples 1 to 5 Electrophotography was carried out in the same manner as in Example 1, except that the known compounds listed in Table 7 were used in place of the pyrazoline compound No. 2 used in Example 1. A photoreceptor was prepared.

[Table] The charging characteristics of the photoreceptor of each example were measured in the same manner as in Example 1. The results are shown in Table 8.

[Table] The durability of each photoreceptor in the comparative example was measured in the same manner as in Example 1. When each photoreceptor was repeatedly charged and exposed, the bright area potential gradually increased and the dark area potential increased. A decrease was observed. In contrast, the photoreceptor of the present invention (Examples 1 to 24)
had high sensitivity, and even after repeated charging and exposure, there was almost no increase in bright area potential and almost no decrease in dark area potential.

Claims (1)

[Scope of Claims] 1. An electrophotographic photoreceptor comprising a layer containing a compound represented by the following general formula []. General formula [] (In the formula, X represents an optionally substituted heterocyclic group selected from the group consisting of a pyridyl group, a quinolyl group, and a carbazolyl group. R ₁ represents _an optionally substituted aryl group. ₃ represents a hydrogen atom or an optionally substituted aryl group.However,
R ₂ and R ₃ are never hydrogen atoms at the same time. _R4
and R ₅ represents a hydrogen atom or an optionally substituted alkyl group or aryl group. however,
R ₄ and R ₅ are never hydrogen atoms at the same time. n
is 0 or 1. Also, when n is 0, R ₄
is never a hydrogen atom. )