JPH04287049A - Bis-styryl compound and electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the compd. which is usable for copying machines printers, etc., as well and is adequate as a carrier transfer material for the photosensitive body having a high sensitivity and high durability and the electrophotographic sensitive body by using a specific compd. CONSTITUTION:This photosensitive body contains the bis-styryl compd. expressed by formula I. In the formula, R<1> denotes 1 to 4C alkyl group, -OR<2> (R<2> is 1 to 4C alkyl group), etc.; Ar<1> to Ar<4> are a heterocyclic group; Ar<1> and Ar<2>, Ar<3> and Ar<4> may respectively cooperatively form a ring. The good images which have the high sensitivity and are free from the generation of screen defects and image defects, such as white dots, black spots, fogging and density degradation, are obtd. when the carrier transfer material consisting of the compd. of the formula I is incorporated as the photosensitive body into the copying machines, printer, etc., and is repetitively used. The good images which are small in residual potential and are free from the generation of the screen defects and image defects are obtd. even if this material is incorporated into the copying machines, printers, etc., and is repetitively used.

Description

[0001] The present invention relates to a bisstyryl compound and an electrophotographic photoreceptor, and particularly to an electrophotographic photoreceptor having a photosensitive layer containing a carrier-generating substance and a carrier-transporting substance. The present invention relates to a bisstyryl compound suitable as the carrier transport material and an electrophotographic photoreceptor. [Prior Art] Conventionally, electrophotographic photoreceptors have been made of selenium,
Photoreceptors containing as a main component an inorganic photoconductor such as zinc oxide, cadmium sulfide, or silicon have been widely known. However, these do not necessarily have satisfactory properties such as thermal stability and durability, and there are also problems in manufacturing and handling. On the other hand, a photoreceptor having a photosensitive layer containing an organic photoconductive compound as a main component is relatively easy to manufacture, inexpensive, and easy to handle, and generally selenium photoreceptors are It has superior thermal stability. Poly-N-vinylcarbazole is well known as such an organic photoconductor compound, and its main component is a charge transfer complex formed from poly-N-vinylcarbazole and a Lewis acid such as 2,4,7-trinitro-9-fluorenone. A photoreceptor having a photosensitive layer has already been put into practical use. On the other hand, photoreceptors are known that have a functionally separated photosensitive layer of a laminated type or a single layer type in which the carrier generation function and the carrier transport function of the photoconductor are assigned to separate materials, respectively. For example, a photoreceptor having a photosensitive layer consisting of a carrier generation layer consisting of a thin amorphous selenium layer and a carrier transport layer containing poly-N-vinylcarbazole as a main component has already been put into practical use. However, poly-N-vinylcarbazole lacks flexibility, and its coating is hard and brittle, causing cracks and
Film peeling easily occurs, and photoreceptors using this have poor durability. Therefore, when adding a plasticizer to improve this drawback, the residual potential increases in the electrophotographic process, and the residual potential accumulates with repeated use.
The fog gradually increases, damaging the copied image. Furthermore, since low-molecular organic photoconductive compounds generally do not have film-forming ability, they are used in combination with a suitable binder, and by selecting the binder type, composition ratio, etc., the physical properties or photosensitive characteristics of the film can be improved. However, the types of organic photoconductive compounds that have high compatibility with binders are limited. In reality, there are only a few types of binders that can be used to construct the photosensitive layer of an electrophotographic photoreceptor. For example, US Pat. No. 3,189,447
The 2,5-bis(p-diethylaminophenyl)-1,3,4-oxadiazole described in the above issue is compatible with binders commonly used as materials for the photosensitive layer of electrophotographic photoreceptors, such as polyester and polycarbonate. is low. In other words, when a photosensitive layer is formed by mixing in the proportions required to improve electrophotographic properties, oxadiazole crystals will precipitate at a temperature of 50°C or higher, resulting in poor electrophotographic properties such as charge retention and sensitivity. It has the disadvantage of decreasing. In contrast, US Pat. No. 3,820,989
The diarylalkane derivatives described in the above issue have few compatibility problems with binders, but they have low stability against light, and when used in photoreceptors for repetitive transfer electrophotography where charging and exposure are repeated, the photosensitive layer The disadvantage is that the sensitivity gradually decreases. [0009] Also, US Pat. No. 3,274,000,
Different types of phenothiazine derivatives are described in Japanese Patent Publication No. 47-36428, but all of them have the drawbacks of low photosensitivity and low stability during repeated use. [0010] Also, JP-A No. 58-65440, JP-A No. 58-65440,
The stilbene compounds described in No. 8-190953 and No. 63-149652 have relatively good charge retention and sensitivity, but are not satisfactory in terms of durability upon repeated use. [0011] On the other hand, Japanese Patent Application Publication Nos. 60-175052, 60-174749, 62-120346,
No. 64-32265, Japanese Patent Application Publication No. 1-106069,
Photoreceptors using a distilbene compound as a carrier transport material, such as No. 1-93746 and No. 1-274154, are photoreceptors that have almost solved the above drawbacks, but they cannot be incorporated into copiers, printers, etc. and used repeatedly. The durability is not satisfactory. In particular, the following four points were problematic. 1) In a high-speed copying machine with a high linear speed, the cycle of charging, exposing, and eliminating static electricity is shortened, so that the residual potential increases significantly during repeated copying. 2) In the case of a copying machine, when copies are repeatedly made, image defects in the form of small white dots (referred to as white spots) occur in solid black areas. 3) In the case of a reversal development printer, a defect has been found in that the exposure potential (VL) increases at low temperatures and the charging potential (VH) decreases with repeated use. 4) Image defects in the form of small black dots in white areas (
(called black spots) are more likely to occur. [0016] As described above, the current situation is that a carrier transporting material having practically satisfactory characteristics for producing an electrophotographic photoreceptor has not yet been found. OBJECTS OF THE INVENTION The object of the present invention is to provide a compound suitable as a carrier transport material for a highly sensitive and highly durable photoreceptor and an electrophotographic photoreceptor that can also be used in copying machines, printers, etc. be. 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,
To provide a compound suitable as a carrier generating substance for a photoreceptor and an electrophotographic photoreceptor whose residual potential does not increase even after repeated charging, exposure, and charge removal. (2) A compound suitable as a carrier transport material for a photoreceptor that does not cause image defects in the form of small white dots (referred to as white spots) in solid black areas even after repeated use when incorporated into a copying machine. and to provide an electrophotographic photoreceptor. (3) When used in a reversal development printer, the exposure potential (V
L ) does not increase, and the charging potential (VH
To provide a compound suitable as a carrier generating substance for a photoreceptor and an electrophotographic photoreceptor that does not cause a decrease in ). (4) To provide a compound suitable as a carrier transport material for a photoreceptor and an electrophotographic photoreceptor in which image defects in the form of small black dots (referred to as black spots) do not occur in white areas. Structure of the Invention and Its Effects: That is, the present invention relates to a bisstyryl compound represented by the following general formula [I] or [II] and an electrophotographic photoreceptor containing this bisstyryl compound. . [I] In this general formula, R1 is an alkyl group having 1 to 4 carbon atoms, -OR2 (R2 is an alkyl group having 1 to 4 carbon atoms), (R3 and R4 are (alkyl group, phenyl group, aralkyl group), halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, cyano group, phenyl group, and aralkyl group, which may be different from each other when l≧2. Ar
1, Ar2, Ar3, Ar4 are heterocyclic groups (R5
, R6, R7 are the same as R1, m≧2, n
When ≧2 and q≧2, they may be different from each other. ), and Ar1 and Ar2, Ar3 and Ar4 may each work together to form a ring. is not the same as l≧1, m≧0, n≧0, and q≧0. } [Chemical formula 6] {However, in this general formula [II], Ar1 , Ar2 ,
Ar3, Ar4 are heterocyclic groups (m=0 to 5, but Ar1, Ar2,
When all of Ar3 and Ar4 are m=0 for three of them and m=1 for one, R5 is an alkyl group having 2 to 4 carbon atoms, -OR2
(R2 is an alkyl group having 2 to 4 carbon atoms), (R3
, R4 is an alkyl group, phenyl group, aralkyl group)
, -CH2COOR8 (R8 is an alkyl group), -
OCOR9 (R9 is an alkyl group, a phenyl group, an aralkyl group), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, an aralkyl group; in other cases, R5 is the number of carbon atoms 1-4 alkyl group, -OR10 (R10 is an alkyl group having 1-4 carbon atoms), (R11, R12 are an alkyl group, phenyl group, aralkyl group), halogen atom, halogenated alkyl group having 1-4 carbon atoms group, cyano group, phenyl group, aralkyl group, n = 0 to 7, q = 0 to 7, R6, R7
is an alkyl group having 1 to 4 carbon atoms, -OR10(R1
0 is the same as above), (R11 and R12 are the same as above), halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, cyano group,
When it is a phenyl group or an aralkyl group, and m≧2, n≧2 or q≧2, the plurality of R5s, the plurality of R6s, and the plurality of R7s may be different from each other. ) and A
r1 and Ar2, Ar3 and Ar4 may each cooperate with each other to form a ring. is not the same as } In the compound of the above general formula according to the present invention, the above substituents R1 to R12 include alkyl groups such as methyl, ethyl, propyl, and butyl; alkoxy groups such as methoxy, ethoxy, and propoxy; fluorine, chlorine,
Halogen atoms such as bromine and iodine; dialkylamino groups such as diethylamine; dialkylamino groups such as diethylphenylamine; diarylamino groups such as diphenylamine; aralkyl groups such as benzyl; phenyl groups; cyano groups; trifluoromethyl groups, etc. can be mentioned. The compounds of the above general formulas [I] and [II] of the present invention have the following characteristics A to C, and are suitable as carrier transport materials for electrophotographic photoreceptors. (A). Since it is a bis-styryl compound with a substituent in the molecule and a pair of styryl groups with an asymmetric structure, it has improved sensitivity and durability, and also reduces fluctuations in charging potential, so it can be incorporated into copiers, printers, etc. When used repeatedly, good images can be obtained without image defects such as white spots, black spots, fogging, and loss of density. (B). Moreover, when incorporated into a high-speed copying machine, printer, etc. and used repeatedly, the residual potential becomes small, so good images without image defects or image defects can be obtained. (C). Since it is a bisstyryl compound, it is easy to synthesize. Specific compound No. of the above general formula [I].
1 to 393 are collectively exemplified below. Next, an example of the synthesis of the compound of general formula [I] will be explained, and an outline of the synthesis recipe is shown below. (Synthesis Example 1: Synthesis of Exemplified Compound 1) A synthesis example of diformyl compound 3 was carried out as follows according to a known method. 4-Methylaniline 1 (manufactured by Tokyo Kasei Co., Ltd.) (1 molar ratio), iodobenzene (manufactured by Tokyo Kagaku Co., Ltd.) (2.5 molar ratio), potassium carbonate (manufactured by Kanto Kagaku Co., Ltd.) (2 molar ratio), and copper powder ( Kanto Kagaku Co., Ltd.) (0.2 molar ratio) was added, and the internal temperature was 1.
The reaction was carried out at 90 to 210 °C for 50 hours, and after post-treatment, column purification was performed to obtain 4-methyltriphenylamine 2 in a yield of 8.
5% (Ullmann reaction). 4-Methyltriphenylamine 2 (1 molar 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) was added, reacted for 24 hours at an internal temperature of 70 to 90°C, and after post-treatment, column purification was performed to obtain N,N-bis(4-formyl-phenyl)-4-methylaniline 3 in a yield of 65%.
(Vilsmeyer reaction). Diethyl phosphonate compound 7 was synthesized as follows according to a known method. 4-Methylbenzophenone 4 (manufactured by Aldrich) (1 molar ratio) was added to methanol (manufactured by Kanto Kagaku), and sodium borohydride (manufactured by Kanto Kagaku) (0.5 molar ratio) was added. Warm 1
The reaction was carried out at 0 to 20°C for 5 hours, and after post-treatment, column purification was performed to obtain hydroxy compound 5 in a yield of 95% (reduction reaction). Hydroxy compound 5 (1 molar ratio) was added to toluene (manufactured by Wako Pure Chemical Industries, Ltd.), thionyl chloride (manufactured by Tokyo Kasei Co., Ltd.) (1.2 molar ratio) was added, and the internal temperature was 10 to 10.
The reaction was carried out at 20° C. for 2 hours, and after post-treatment, the chloride 6 was obtained in a yield of 95% (substitution reaction). Triethyl phosphite (manufactured by Kanto Kagaku Co., Ltd.) (1.2 molar ratio) was added to the chloride 6 (1 molar ratio) and reacted for 10 hours at an internal temperature of 140 to 160°C, followed by distillation and purification after post-treatment. As a result, diethyl phosphonate 7 was obtained in a yield of 93% (diethylation reaction of phosphonate). The diethyl phosphonate compound 12 was synthesized as follows according to a known method. Benzophenone 9 (manufactured by Tokyo Kagaku Co., Ltd.) (1 molar ratio) was added to methanol (manufactured by Kanto Kagaku Co., Ltd.), and sodium borohydrite (manufactured by Kanto Kagaku Co., Ltd.) (0.5 molar ratio) was added, and the mixture was heated to an internal temperature. 5 at 10-20℃
The reaction was carried out for a period of time, and after post-treatment, column purification was performed to obtain hydroxy compound 10 in a yield of 93% (reduction reaction). Hydroxy compound 10 (1 molar ratio) was added to toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and thionyl chloride (
(manufactured by Tokyo Kasei Co., Ltd.) (1.2 molar ratio), and the internal temperature was 10.
The reaction was carried out at ~20°C for 2 hours, and after post-treatment, chloride 11 was obtained in a yield of 96% (substitution reaction). Triethyl phosphite (manufactured by Kanto Kagaku Co., Ltd.) (1.2 molar ratio) was added to the chloride 11 (1 molar ratio),
Reaction was carried out at an internal temperature of 140 to 160 °C for 10 hours, and after post-treatment, distillation purification was performed to obtain diethyl phosphonate 12 in a yield of 91%.
(phosphonic acid diethylation reaction). Synthesis of CTM was carried out as follows using the compound obtained as described above as a raw material. N,N-bis(4-formyl-phenyl)-4-methylaniline 3
0.33 mol and 1-(4-methyl-phenyl)-1-
70.033 mol of diethyl phenyl-methylphosphonate, and 50 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.)
dissolved in Sodium methoxide (manufactured by Kanto Kagaku Co., Ltd.)
Put 0.033 mol in 50 ml of toluene and cool on ice.
This solution was added to the above solution while keeping the internal temperature below 25°C. Thereafter, the mixture was stirred at room temperature for 3 hours. 100ml water
was added, the toluene layer was washed with water, water was removed from the toluene layer with sodium sulfate (manufactured by Kanto Kagaku Co., Ltd.), the solvent was distilled off, the resulting residue was purified on a silica column, and the monoform 8 was purified to a yellowish white color. It was obtained as crystals in a yield of 41% (0.014 mol). Next, 80.033 mol of formyl compound and 12 mol of diethyl 1,1-diphenyl-methylphosphonate
0.066 mol was dissolved in 50 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.). 0.066 mol of sodium methoxide (manufactured by Kanto Kagaku Co., Ltd.) was added to 50 ml of toluene, and this solution was added to the above solution under ice cooling while keeping the internal temperature below 25°C. Thereafter, the mixture was stirred at room temperature for 3 hours. water 1
00 ml was added, the toluene layer was washed with water, water was removed from the toluene layer with sodium sulfate (manufactured by Kanto Kagaku Co., Ltd.), the solvent was distilled off, the resulting residue was purified with a silica column, and the desired example was purified. Compound 1 was obtained as yellow-white crystals in a yield of 71% (0.023 mol). The melting point was 125°C, and the elemental analysis values were as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
91.41 6.35
2.18 Calculated value (%): 91.54
6.24 2.22
IR data of Exemplary Compound 1 (spectrum in Figure 1) 1
501cm-1/S (Strong: same below) 0
(Synthesis Example 2: Synthesis of Exemplified Compound 10) In Synthesis Example 1, 4-methylaniline was replaced with 2,4,6-trimethylaniline, benzophenone was replaced with 4,4'-dimethylbenzophenone, and 4-methylaniline was replaced with 4,4'-dimethylbenzophenone. Synthesis was carried out in the same manner as in Synthesis Example 1, except that benzophenone was replaced with 2,4-dimethylbenzophenone, and Exemplified Compound 10 was obtained as yellow-white crystals in a yield of 59% (0.019 mol). The melting point was 145-147°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) Measured value (%):
90.78 7.08
2.01 Calculated value (%): 90.9
4 7.06 2
．． 00 [0043] (Synthesis Example 3: Exemplary Compound 8
Synthesis of 5) Synthesis was performed in the same manner as in Synthesis Example 1, except that 4-methylaniline was replaced with 4-chloroaniline, and Exemplified Compound 85 was synthesized as yellow-white crystals in a yield of 65%.
．． 0.21 moles were obtained. The melting point was 142-144°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) Measured value (%):
86.80 5.60
2.10 Calculated value (%): 86
．． 81 5.58
2.15 (Synthesis Example 4: Exemplary Compound 1
Synthesis of 96) In Synthesis Example 1, 4-methylaniline was converted to 2,
Synthesis was carried out in the same manner as in Synthesis Example 1, except that 4-dimethoxyaniline was replaced with 4-methoxybenzophenone, and 0.018 mol of Exemplified Compound 196 was obtained as yellow-white crystals in a yield of 55%. Ta. The melting point was 120-126°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
85.00 6.00
2.00 Calculated value (%): 85.0
7 5.97 2
．． (Synthesis Example 5: Synthesis of Exemplified Compound 298) In Synthesis Example 1, 4-methylaniline was replaced with 4-phenylaniline, benzophenone was replaced with 4-iodobenzophenone, and 4-methylbenzophenone was replaced with 2,4 Synthesis was carried out in the same manner as in Synthesis Example 1 except that -dimethylbenzophenone was used, and 0.021 mol of Exemplary Compound 298 was obtained as yellow-white crystals in a yield of 65%. The melting point was 131-134°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
77.62 5.01
1.52 Calculated value (%
): 77.84 4.9
3 1.71 Next, specific compound No. 3 of the above general formula [II]. (1)～
(104) are collectively illustrated below. Next, an example of the synthesis of the compound of general formula [II] will be explained, and the outline of the synthesis recipe is shown below. (Synthesis Example 6: Synthesis of Exemplified Compound (1)) Diformyl compound 3 was synthesized as follows according to a known method. Aniline 1 (Kanto Kagaku Co., Ltd.) (1 molar ratio), iodobenzene (Tokyo Kagaku Co., Ltd.) (2.5 molar ratio), potassium carbonate (Kanto Kagaku Co., Ltd.) (2 molar ratio), and copper powder (Kanto Kagaku Co., Ltd.) (0.2 molar ratio) was added, and the internal temperature was 190 to 2.
The reaction was carried out at 10° C. for 50 hours, and after post-treatment, column purification was performed to obtain triphenylamine 2 in a yield of 81% (Ullmann reaction). Triphenylamine 2 (1 molar ratio) contains N,
N-dimethyl formaldehyde (manufactured by Kanto Kagaku Co., Ltd.) (4 molar ratio) and phosphorus oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) (3 molar ratio) were added, reacted for 24 hours at an internal temperature of 70 to 90°C, and after post-treatment. After column purification, N,N-bis(4-formyl-
Phenyl)-2,4-methylaniline 3 was obtained in a yield of 53% (Vilsmeier reaction). The diethyl phosphonate was synthesized as follows according to a known method. 4-methylbenphenone 4 (manufactured by Aldrich) (1 molar ratio) was placed in methanol (manufactured by Kanto Kagaku), and sodium borohydride (manufactured by Kanto Kagaku) (0.5 molar ratio) was added. Internal temperature 10~
The reaction was carried out at 20° C. for 5 hours, and after post-treatment, column purification was performed to obtain hydroxy compound 5 in a yield of 95% (reduction reaction). Hydroxy compound 5 (1 molar ratio) was added to toluene (manufactured by Wako Pure Chemical Industries, Ltd.), thionyl chloride (manufactured by Tokyo Kasei Co., Ltd.) (1.2 molar ratio) was added, and the internal temperature was 10 to 10.
The reaction was carried out at 20° C. for 2 hours, and after post-treatment, the chloride 6 was obtained in a yield of 95% (substitution reaction). [0055] Triethyl phosphite (manufactured by Kanto Kagaku Co., Ltd.) (1.2 molar ratio) was added to the chloride 6 (1 molar ratio) and reacted for 10 hours at an internal temperature of 140 to 160°C, followed by distillation and purification after post-treatment. As a result, diethyl phosphonate compound 7 was obtained in a yield of 93% (diethylation reaction of phosphonate). Diethyl phosphonate compound 12 was synthesized as follows according to a known method. 4,4'-dimethylbenzophenone (manufactured by Aldrich) (1 molar ratio) was placed in methanol (manufactured by Kanto Kagaku), and sodium borohydrite (manufactured by Kanto Kagaku) (0.5 molar ratio) was added. In addition, the reaction was carried out at an internal temperature of 10 to 20° C. for 5 hours, and after post-treatment, column purification was performed to obtain hydroxy compound 10 in a yield of 91% (reduction reaction). Hydroxy compound 10 (1 molar ratio) was added to toluene (manufactured by Wako Pure Chemical Industries, Ltd.), and thionyl chloride (
(manufactured by Tokyo Kasei Co., Ltd.) (1.2 molar ratio), and the internal temperature was 10.
The reaction was carried out at ~20°C for 2 hours, and after post-treatment, chloride 11 was obtained in a yield of 95% (substitution reaction). Triethyl phosphite (manufactured by Kanto Kagaku Co., Ltd.) (1.2 molar ratio) was added to chloride 11 (1 molar ratio),
Reaction was carried out at an internal temperature of 140 to 160 °C for 10 hours, and after post-treatment, distillation purification was performed to obtain diethyl phosphonate 12 in a yield of 90%.
(phosphonic acid diethylation reaction). Synthesis of CTM was carried out as follows using the compound obtained as described above as a raw material. N,N-bis(4-formyl-phenyl)-aniline-3 0.3
3 mol and 0.033 mol of diethyl 1-(4-methyl-phenyl)-1-phenyl-methylphosphonate 7 were dissolved in 50 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.). Sodium methoxide (manufactured by Kanto Kagaku Co., Ltd.) 0.033
Place the mole in 50 ml of toluene and bring the internal temperature to 25°C under ice cooling.
This solution was added to the above solution while maintaining the following: Thereafter, the mixture was stirred at room temperature for 3 hours. Add 100 ml of water, wash the toluene layer with water, remove water from the toluene layer with sodium sulfate (manufactured by Kanto Kagaku Co., Ltd.), evaporate the solvent, and purify the resulting residue with a silica column to obtain monoform 8. It was obtained as yellow-white crystals in a yield of 38% (0.013 mol). Next, 80.033 moles of the formyl compound and 12 0.066 moles of diethyl 1,1-bis-(4-methylphenyl)-methylphosphonate were dissolved in 50 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.). 0.066 mol of sodium methoxide (manufactured by Kanto Kagaku Co., Ltd.) was added to 50 ml of toluene, and this solution was added to the above solution under ice cooling while keeping the internal temperature below 25°C. Then at room temperature 3
Stir for hours. Add 100 ml of water, wash the toluene layer with water, remove water from the toluene layer with sodium sulfate (manufactured by Kanto Kagaku Co., Ltd.), evaporate the solvent, and purify the resulting residue with a silica column. Exemplary compound (1)
was obtained as yellow-white crystals in a yield of 82% (0.027 mol). The melting point was 131-132°C, and the elemental analysis values were as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
91.25 6.51
2.11 Calculated value (%): 91.41
6.42 2.18
(Synthesis Example 7: Synthesis of Exemplified Compound (6)) In Synthesis Example 6, 4-methylbenzophenone was replaced with benzophenone, and 4,4'-dimethylbenzophenone was replaced with 3-methylbenzophenone.
,4-dimethylbenzophenone was used, the synthesis was carried out in the same manner as in Synthesis Example 6, and exemplified compound (6) was obtained as yellowish-white crystals in a yield of 75% (0.025 mol). The melting point was 128-131°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) Measured value (%):
91.51 6.25
2.20 Calculated value (%): 91.5
4 6.24 2
．． 22 [0064] (Synthesis Example 8: Exemplary compound (
Synthesis of 20)) The exemplified compound ( 20) was obtained as yellow-white crystals in an amount of 0.023 mol with a yield of 69%. The melting point was 133-137°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
86.73 5.40
2.19 Calculated value (%): 86.8
4 5.39 2
．． 20 Synthesis Example 9: Exemplary Compound (45
)) In Synthesis Example 6, 4-methylbenzophenone was converted into 4
Synthesis was carried out in the same manner as in Synthesis Example 6, except that 4,4'-dimethylbenzophenone was replaced with -methoxybenzophenone and 3,4-dimethylbenzophenone, and exemplified compound (45) was produced as yellow-white crystals in a yield of 65%. (0.021
mol). The melting point was 131-133°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
89.01 6.30
2.10 Calculated value (%): 89.1
9 6.26 2
．． 12 (Synthesis Example 10: Synthesis of Exemplified Compound (81)) Synthesis was carried out in the same manner as in Synthesis Example 6, except that 4,4'-dimethylbenzophenone was replaced with 2-benzoylnaphthalene. Exemplary compound (81)
was obtained as yellow-white crystals in a yield of 67% (0.022 mol). The melting point was 135-137°C, and the elemental analysis was as follows. C (carbon)
H (hydrogen) N (nitrogen) measurement value (%):
91.61 6.21
2.05 Calculated value (%): 91.72
6.19 2.1
[0071] Electrophotographic photoreceptors containing the above-mentioned compound of general formula [I] as a carrier transporting substance are shown in FIGS.
It can take the form shown in FIG. That is, in FIGS. 2 and 3, the conductive support 1
A carrier generation layer 2 containing a carrier generation substance as a main component on top
and a carrier transport layer 3 containing the carrier transport substance according to the present invention as a main component. As shown in FIGS. 4 and 5, the photosensitive layer 4 may be provided on the conductive support 1 with an intermediate layer 5 interposed therebetween. When the photosensitive layer 4 has a two-layer structure as described above, a photosensitive member having excellent electrophotographic properties can be obtained. Further, in the present invention, as shown in FIGS. 6 and 7, a photosensitive layer 4 comprising a carrier-generating substance dispersed in a layer 6 containing a carrier-transporting substance as a main component is placed on a conductive support 1. It may be provided directly or via the intermediate layer 5. Further, in the present invention, a protective layer 7 may be provided as the outermost layer as shown by the imaginary line in FIG. Since the compound of general formula [I] in the present invention has poor coating-forming ability by itself, a photosensitive layer is formed by combining various binders. Any binder can be used here, but it is hydrophobic and has a high dielectric constant.
It is preferable to use an electrically insulating film-forming polymer. Examples of such high molecular weight polymers include, but are not limited to, the following. (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-vinylcarzole (P-18) Polyvinyl butyral (P-19) Polyvinyl formal 00
[80] These binder resins can be used alone or as a mixture of two or more. CTMs that can be used in combination in the present invention
There are no particular limitations on the derivative, but examples include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives,
Bisimidazolidine derivatives, styryl compounds, hydrazone compounds, pyrazoline derivatives, amine derivatives, oxazolone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives,
Acridine derivatives, phenazine derivatives, aminostilbene derivatives, poly-N-vinylcarbazole, poly-1-
These include vinylpyrene, poly-9-vinylanthracene, and the like. The CTM used in the present invention is preferably one that not only has an excellent ability to transport holes generated during light irradiation to the support side, but also is suitable for combination with the organic pigment used in the present invention, which will be described later. . Examples of the carrier-generating substance used in the carrier-generating layer of the photosensitive layer according to the present invention include the following: (1) Azo dyes such as monoazo dyes, bisazo dyes, and trisazo dyes ( 2) Perylene dyes such as perylenic anhydride and perylenic acid imide (3) Indigo dyes such as indigo and thioindigo (
4) Polycyclic quinones such as anthraquinone, pyrenequinone, and flavanthrones (5) Quinacridone dyes (6) Bisbenzimidazole dyes (7) Induthrone dyes (8) Squarylium dyes (9) Cyanine dyes (10) Azulenium pigments (11) Triphenylmethane pigments (12) Amorphous silicon (13) Phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine (14) Selenium, selenium-tellurium, selenium-arsenic (15)
) CdS, CdSe (16) Pyrylium salt dyes, thiapyrylium salt dyes, etc. can be mentioned, and they can be used alone or as a mixture of two or more types. In the electrophotographic photoreceptor according to the present invention,
It is preferable to use organic pigments such as fluorenone-based bisazo pigments, fluorenylidene-based bisazo pigments, and polycyclic quinone pigments as the CGM. In particular, the general formula shown below [
When the fluorenone-based bisazo pigment, fluorenylidene-based bisazo pigment, and polycyclic quinone pigment of [F1] are used in the present invention, they exhibit significantly improved effects in terms of sensitivity, durability, image quality, etc. Specific examples (F1-1 to F1-24) of fluorenone bisazo pigments that can be used in the present invention are listed below, but the invention is not limited thereto. General formula [F1] below that can be used in the present invention
The fluorenone-based bisazo pigment represented by
It is synthesized by a method such as No. 2. The fluorenylidene bisazo pigment that can be used in the present invention is represented by the general formula [F2] below. Specific examples of the bisazo pigments represented by the general formula [F2] that are effective in the present invention include those represented by the structural formulas (F2-1 to F2-7) shown below. This does not limit the bisazo pigments that can be used in the present invention. The polycyclic quinone pigments that can be used in the present invention are represented by the following general formulas [Q1] to [Q3]. Specific examples of the polycyclic quinone pigments usable in the present invention represented by the general formulas [Q1] to [Q3] shown below are shown below, but the invention is not limited thereto. Specific compound examples (Q1-1 to Q1-6) of the anthantrone pigment represented by the general formula [Q1]
These are listed below. Specific compound examples of dibenzpyrenequinone pigments represented by the general formula [Q2] (Q2 -1 to Q2 -
5) is listed below. Specific compound examples (Q3-1 to Q3-4) of the pyranthrone pigment represented by the general formula [Q3] are listed below. General formulas [Q1] to [Q1] that can be used in the present invention
The polycyclic quinone pigment represented by Q3 can be easily synthesized by a known method. As the metal-free phthalocyanine pigment that can be used in the present invention, all metal-free phthalocyanines and their derivatives having photoconductivity can be used, but for example, α
type, β type, τ, τ' type, η, η' type, Χ type, and the crystal forms described in JP-A-62-103651 and derivatives thereof, etc. can be used. In particular, it is desirable to use τ, Χ, and K/R-Χ types. The Χ-type metal-free phthalocyanine is described in US Pat. No. 3,357,989, and the τ-type metal-free phthalocyanine is described in JP-A-58-182639. [0098] K/R-X type is disclosed in Japanese Patent Application Laid-Open No. 62-103651.
As stated in the issue, at the Bragg angle (2θ ± 0.2 degrees) for CuKa, 1.541 Å, 7
．． 7, 9.2, 16.8, 17.5, 22.4,
It has a main peak at 28.8 degrees, and the ratio of the peak intensity at 16.8 degrees to the peak intensity at 9.2 degrees is 0.8.
~1.0 and 28.8 for 22.4 degrees
It is a phthalocyanine characterized by having a peak intensity ratio of 0.4 or more. Oxytitanyl phthalocyanine that can be used in the present invention is represented by the general formula [TP] below. [0100] As those which can be used in the present invention, those having different crystal forms disclosed in the following patents are known. 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. 2-215866, and the like. Dispersion media for organic pigments that can be used in the present invention include known dispersion media such as methyl ethyl ketone. In the present invention, the photosensitive layer may contain one or more known electron-accepting substances. The addition ratio of the electron-accepting substance is as follows: organic pigment used in the present invention:electron-accepting substance=100:0.
01-200, preferably 100:0.1-10
It is 0. In addition, the addition ratio of the electron-accepting substance is an important ratio of total CTM:electron-accepting substance=100:0.01 to 1.
00, preferably 100:0.1 to 50. Further, organic amines can be added to the photosensitive layer for the purpose of improving the charge generation function of CGM (carrier generating substance), and it is particularly preferable to add a secondary amine. These compounds are disclosed in JP-A No. 59-218447,
It is described in No. 62-8160. Further, in the photosensitive layer, for the purpose of preventing ozone deterioration, an antioxidant disclosed in JP-A-63-18354, for example, can be added. The amount of antioxidant added is CTM
The amount is from 0.1 to 100 parts by weight, preferably from 1 to 50 parts by weight, particularly preferably from 5 to 25 parts by weight, per 100 parts by weight. The photoreceptor according to the present invention may also contain an ultraviolet absorber or the like for the purpose of protecting the photosensitive layer, if necessary, or a dye for correcting color sensitivity. An intermediate layer may be provided between the photosensitive layer and the support, and this intermediate layer functions as an adhesive layer, a blocking layer, or the like. In the present invention, when the photosensitive layer has a two-layer structure as shown in FIG. 2, the CGL (carrier generation layer) is placed directly on the conductive support or the CTL (carrier transport layer) or as an adhesive layer as required. Alternatively, it can be formed by the following method after providing an intermediate layer such as a blocking layer. (1) Vacuum deposition method (2) Method of applying a solution of CGM dissolved in a suitable solvent. (3) CGM is formed into fine particles in a dispersion medium using a ball mill, sand grinder, etc. A method of applying a dispersion obtained by mixing and dispersing with a binder, if necessary. Specifically, any vapor deposition method such as vacuum evaporation, sputtering, CVD, or coating method such as dipping, spray, blade, or roll method may be used. The thickness of the CGL thus formed is preferably 0.01 μm to 5 μm, more preferably 0.05 μm to 3 μm. [0113] Furthermore, CTL can also be formed by the same method as CGL. Although the thickness of the CTL can be changed as necessary, it is usually preferably 5 μm to 60 μm. [0114] The composition ratio in this CTL is preferably 0.1 to 5 parts by weight of the binder to 1 part by weight of the CTM of the present invention, but when forming the photosensitive layer 4 in which fine particulate CGM is dispersed, It is preferable to use the binder in an amount of 5 parts by weight or less per 1 part by weight of CGM. Further, when the CTL is configured as a dispersed type in a binder, it is preferable to use the binder in an amount of 5 parts by weight or less per 1 part by weight of the CGM. [0115] The electrophotographic photoreceptor according to the present invention has the above-mentioned structure, and as is clear from the examples described later, it has excellent charging characteristics, sensitivity characteristics, image forming characteristics, etc.
In particular, it shows little fatigue deterioration even after repeated use, and has excellent durability. Furthermore, the electrophotographic photoreceptor according to the present invention can be used not only in electrophotographic copying machines but also in a wide range of application fields such as photoreceptors for printers using lasers, cathode ray tubes (CRTs), and light emitting diodes (LEDs) as light sources. Can be done. Furthermore, the present invention can be applied to EL (electroluminescence) and the like in addition to such photoreceptors. [Examples] Examples of the present invention will be specifically described below, but the embodiments of the present invention are not limited thereto. Example 1 30 g of polyamide copolymerized with a monomer composition of ε-amino-caproic acid, adipic acid and N-(β-aminoethyl)piperazine in a ratio of 1:1:1 was heated to 50°C. It was added to 800 ml of methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.). Thereafter, it was applied by dip coating onto an animinium drum having a diameter of 80 mm to form an intermediate layer having a thickness of 0.6 μm. Next, 20 g of fluorenone bisazo pigment (exemplified compound F1-23) was used as CGM, and polyvinyl butyral resin S-LEC BX-1 was used as a binder.
(manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 1000 ml of methyl ethyl ketone (manufactured by Kanto Chemical Co., Ltd., EL standard) and milled in a sand mill for 24 hours to obtain a CGL coating liquid. This was coated by dip coating on the above intermediate layer to give a thickness of 0.2 μm.
GL was formed. [0120] Thereafter, exemplified compound 1140 was used as CTM.
g and polycarbonate resin “Iupilon Z-200”
(manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 1000 ml of 1,2-dichloroethane special grade (manufactured by Kanto Chemical Co., Ltd.) to obtain a CTL coating liquid. [0121] 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, a photoreceptor 1 was produced in which the intermediate layer-CGL-CTL were sequentially laminated. Examples 2 to 10 Photoreceptors 2 to 10 were prepared in the same manner as in Example 1 except that CGM and CTM in Example 1 were used as exemplified compounds as shown in Table 1 below.
It was created. Comparative Examples 1 and 2 As shown in Table 1 below, comparative photoreceptors were prepared in the same manner as in Example 1, except that the CTM of Example 1 was replaced with Comparative Compounds (1) and (2) described below. did. Example 11 The intermediate layer was formed in the same manner as in Example 1. 20 g of polycyclic quinone pigment (exemplary compound; Q1-3) as CGM and 10 g of polycarbonate resin C-1300 (manufactured by Teijin Chemicals) as a binder.
was dissolved in special grade 1,2-dichloroethane (manufactured by Kanto Kagaku Co., Ltd.), and milled in a ball mill for 30 hours to obtain a CGL coating 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, CTL was laminated in the same manner as in Example 1 except that Exemplary Compound 2 was used as CTM to prepare photoreceptor 11. Examples 12 to 20 Photoreceptor 12 was prepared in the same manner as in Example 1 except that CGM and CTM in Example 11 were used as exemplified compounds as shown in Table 2 below.
~20 were created. Comparative Examples 3 and 4 Comparative photoreceptors 3 and 4 were prepared in the same manner as in Example 11, except that CTM was used as Comparative Compounds (1) and (2) in Example 11, as shown in Table 2 below. did. Example 21 After dissolving 12 g of polyvinyl butyral resin (S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 1000 ml of ethyl ethyl ketone, exemplified compound Q1-3;5 was used as CGM.
．． 7 g of Exemplified Compound F1-23; 0.5 g were mixed and dispersed with a sand grinder for 12 hours. This was applied by dip coating onto the intermediate layer described in Example 1 to form CGL, and CTL was formed in the same manner as in Example 1 except that CTM was changed to the exemplified compound shown in Table 3. Body 21 was created. Examples 22 to 30 Photoreceptor 22 was prepared in the same manner as in Example 1 except that CGM and CTM in Example 11 were used as exemplified compounds as shown in Table 3 below.
~30 were created. Comparative Examples 5 and 6 As shown in Table 3 below, comparative photoreceptors 5 and 6 were prepared in the same manner as in Example 21, except that CTM was used as Comparative Compounds (1) and (2) in Example 21. did. Example 31 50 g of the polyamide used in Example 1 was poured into 800 ml of methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.) heated to 50° C. and dissolved. After cooling to room temperature, 200 ml of 1-butanol 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. Next, as CGM, 40 g of τ-type metal-free phthalocyanine (τ-Pc) was added to silicone resin “KR-52”.
Methyl ethyl ketone EL standard (manufactured by Kanto Chemical Co., Ltd.) in which 200 g of "40" (solid content 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved
In addition to 2000 ml, the mixture was dispersed for 4 hours using a sand grinder to obtain a CGL coating liquid. This was dip coated onto the above intermediate layer to form a 0.4 μm thick CGL. Thereafter, 135 g of Exemplified Compound 6 and 165 g of polycarbonate "Iupilon Z-200" (Mitsubishi Gas Chemical Co., Ltd.) were mixed with 1,2-dichloroethane special grade (
Kanto Kagaku Co., Ltd.) was dissolved in 1000 ml to obtain a CTL coating liquid. This was coated on the above CGL by dip coating, and then dried at 100° C. for 1 hour to obtain a CTL with a thickness of 22 μm. A photoreceptor was prepared by laminating an intermediate layer, CGL, and CTL in this order. Examples 32 to 40 Photoreceptors 32 to 40 were prepared in the same manner as in Example 31, except that CGM was changed to the exemplified compounds shown in Table 4 below.
It was created. Comparative Examples 7 and 8 As shown in Table 4 below, comparative photoreceptors were prepared in the same manner as in Example 31, except that CTM was used as Comparative Compounds (1) and (2). Example 41 Intermediate layer-CGL-CT was prepared in the same manner as in Example 1 except that X-type metal-free phthalocyanine (X-Pc) was used for CGM.
A photoreceptor was prepared by sequentially laminating L. Examples 42 to 50 Photoreceptors 42 to 50 were prepared in the same manner as in Example 41, except that CTM was changed to the exemplified compounds shown in Table 5 below.
It was created. Comparative Examples 9 and 10 As shown in Table 5 below, comparative photoreceptors were prepared in the same manner as in Example 41, except that CTM was used as Comparative Compounds (1) and (2). Example 51 Y-type oxytitanium phthalocyanine (Y-T
iOPC) [Journal of Electrophotography Society 250(2), 29(
2), 1990], a photoreceptor was prepared in the same manner as in Example 1, in which the intermediate layer, CGL, and CTL were sequentially laminated. Examples 52 to 60 Photoreceptors 52 to 60 were prepared in the same manner as in Example 51 except that CTM was changed to the exemplified compounds shown in Table 6 below.
It was created. Comparative Examples 11 and 12 As shown in Table 6 below, comparative photoreceptors were prepared in the same manner as in Example 51, except that CTM was replaced with Comparative Compounds (1) and (2). Example 61 A photoreceptor was prepared by sequentially laminating the intermediate layer, CGL, and CTL in the same manner as in the above example except that fluorenylidene-based azo CGM was used as the CGM. Examples 62 to 70 Photoreceptor 62 was prepared in the same manner as in Example 61 except that CGM and CTM in Example 61 were used as exemplified compounds as shown in Table 7 below.
~70 were created. Comparative Examples 13 to 14 As shown in Table 7 below, comparative photoreceptors were prepared in the same manner as in Example 61, except that CTM was used as Comparative Compounds (1) to (2). Example 71 30 g of polyamide copolymerized with a monomer composition of ε-amino-caproic acid, adipic acid and N-(β-aminoethyl)piperazine in a ratio of 1:1:1 was heated to 50°C. It was added to 800 ml of methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.). Thereafter, it was applied by dip coating onto an animinium drum having a diameter of 80 mm to form an intermediate layer having a thickness of 0.6 μm. Next, 20 g of fluorenone disazo pigment (exemplified compound F1-23) was used as CGM, and polyvinyl butyral resin S-LEC BX-1 was used as a binder.
(manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 1000 ml of methyl ethyl ketone (manufactured by Kanto Chemical Co., Ltd., EL standard) and milled for 24 hours in a sand mill to obtain a CGL coating liquid. This was coated by dip coating on the above intermediate layer to give a thickness of 0.2 μm.
GL was formed. [0150] Thereafter, 140 g of exemplified compound (1) and 165 g of polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were dissolved in 1000 ml of 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.).
A TL coating liquid was obtained. This was coated on the CGL by dip coating and dried at 100° C. for 1 hour to form a CTL with a thickness of 23 μm. In this way, a photoreceptor 71 was produced in which the intermediate layer-CGL-CTL were sequentially laminated. Examples 72 to 80 Photoreceptor 72 was prepared in the same manner as in Example 71 except that CGM and CTM in Example 71 were used as exemplified compounds as shown in Table 8 below.
~80 were created. Comparative Examples 15 to 16 As shown in Table 8 below, comparative photoreceptors were prepared in the same manner as in Example 71, except that the CTM in Example 71 was replaced with the comparative compounds (1) to (2) described below. did. Example 81 The intermediate layer was formed in the same manner as in Example 71. As CGM, polycyclic quinone pigment (exemplary compound; Q1-3) 20
g and polycarbonate resin C-1 as a binder
300 (manufactured by Teijin Kasei Co., Ltd.) was dissolved in 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.), and 30 g was dissolved in a ball mill.
Time milling was performed to obtain a CGL coating solution. This was dip coated onto the intermediate layer to form a CGL with a thickness of 0.6 μm. Next, CTL was laminated in the same manner as in Example 71 except that CTM was used as the exemplified compound (2), and the photoreceptor 81
It was created. Examples 82 to 90 Photoreceptor 8 was prepared in the same manner as in Example 71 except that CGM and CTM in Example 81 were used as exemplified compounds as shown in Table 9 below.
2 to 90 were created. Comparative Examples 17-18 As shown in Table 9 below, comparative photoreceptors 17-18 were prepared in the same manner as in Example 71, except that CTM was used as Comparative Compounds (1) to (2) in Example 71. did. Example 91 After dissolving 12 g of polyvinyl butyral resin (S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 1000 ml of ethyl ethyl ketone, exemplified compound Q1-3 was prepared as CGM;
5.7 g and 0.5 g of Exemplary Compound F1-23 were mixed and dispersed with a sand grinder for 12 hours. [0158] This was applied by dip coating on the intermediate layer described in Example 71 to form CGL, and then CGL was coated in the same manner as in Example 71.
A photoreceptor 91 was produced by forming a TL. Examples 92 to 100 Photoreceptors 92 to 100 were prepared in the same manner as in Example 91, except that CGM and CTM were used as exemplified compounds as shown in Table 10 below. Comparative Examples 19-20 As shown in Table 10 below, comparative photoreceptors 19-20 were prepared in the same manner as in Example 91 except that CTM was used as Comparative Compounds (1) to (2) in Example 91. did. Example 101 800 ml of methanol EL standard (manufactured by Kanto Kagaku Co., Ltd.) was prepared by heating 50 g of the polyamide used in Example 71 to 50°C.
and dissolved. After cooling to room temperature, 200 ml of 1-butanol special grade (manufactured by Kanto Kagaku Co., Ltd.) was added. After that, it was applied by dip coating onto an aluminum drum with a diameter of 80 mm.
An intermediate layer of 0.5 μm was formed. Next, as CGM, 40 g of τ-type metal-free phthalocyanine (τ-Pc) was mixed with silicone resin “KR-5”.
240” (solid content 20%) (manufactured by Shin-Etsu Chemical Co., Ltd.) 200 g
The mixture was added to 2000 ml of methyl ethyl ketone EL standard (manufactured by Kanto Kagaku Co., Ltd.) in which the mixture was dissolved and dispersed for 4 hours using a sand grinder to obtain a CGL coating liquid. This was dip coated on the intermediate layer to form a 0.4 μm thick CGL. [0163] Thereafter, 135 g of exemplified compound (2) and 165 g of polycarbonate "Iupilon Z-200" (Mitsubishi Gas Chemical Co., Ltd.) were dissolved in 1000 ml of 1,2-dichloroethane special grade (manufactured by Kanto Kagaku Co., Ltd.) to prepare a CTL coating liquid. I got it. After applying this by dip coating on the above CGL,
Drying was performed at ℃ for 1 hour to obtain a 22 μm thick CTL. A photoreceptor was prepared by laminating an intermediate layer, CGL, and CTL in this order. Examples 102 to 110 Photoreceptors 102 to 110 were prepared in the same manner as in Example 101, except that CTM was used as an exemplified compound as shown in Table 11 below. Comparative Examples 21-22 As shown in Table 11 below, comparative photoreceptors were prepared in the same manner as in Example 101, except that Comparative Compounds 21-22 were used as CTMs in Example 101. Example 111 Intermediate layer-CGL-C
A photoreceptor was prepared by sequentially laminating TLs. Examples 112 to 120 Photoreceptors 112 to 120 were prepared in the same manner as in Example 111, except that CTM was used as an exemplified compound as shown in Table 12 below. Comparative Examples 23 to 24 As shown in Table 12 below, comparative photoreceptors were prepared in the same manner as in Example 111 except that CTM was replaced with Comparative Compounds (1) to (2). Example 121 Y-type oxytitanium phthalocyanine (TiO
Example 112, except that PC) (described above) was used.
A photoreceptor was prepared by sequentially laminating the intermediate layer-CGL-CTL in the same manner as above. Examples 122 to 130 Photoreceptors 122 to 130 were prepared in the same manner as in Example 121, except that CTM was used as an exemplified compound as shown in Table 13 below. Comparative Examples 25 to 26 As shown in Table 13 below, comparative photoreceptors were prepared in the same manner as in Example 121, except that CTM was replaced with Comparative Compounds (1) to (2). Example 131 An intermediate layer-CGL-CTL was prepared in the same manner as in Example 111 except that fluorenylidene-based azo CGM was used as the CGM.
A photoreceptor was created by sequentially laminating the following materials. Examples 132 to 140 Photoreceptors 132 to 140 were prepared in the same manner as in Example 131 except that CGM and CTM were used as exemplified compounds as shown in Table 14 below. Comparative Examples 27 to 28 As shown in Table 14 below, comparative photoreceptors were prepared in the same manner as in Example 131 except that CTM was replaced with Comparative Compounds (1) to (2). [0175] [0176] [0177] [0178] [0179] [0180] [0181] [0182] [0183] [0184] [0185] [0186] [0187] [0188] [0189] [0190] 0191 [0192] [0193] [0194] [0195] (Evaluation Example 1) Using a modified copying machine U-Bix5076 manufactured by Konica Corporation (charging electrode changed to negative charging, exposure amount 4.65 lux), the linear velocity was 240,
330, 440 mm/sec and 3 steps, 2
The residual potential Vr was measured after repeating charging and exposure ten thousand times. The results are shown in Tables 8 to 10 below, and the photoreceptor using the CTM of the present invention does not have a larger residual potential when the linear velocity is increased than the photoreceptor using the comparative compound, and has excellent high-speed performance. showed that. The initial blank potential (Vw) is shown in Table-1.
5 to 17. (Evaluation Example 2) Using the same modified Konica Co., Ltd. copying machine U-Bix 5076 as used in Evaluation Example 1, a continuous copy test was conducted 100,000 times using recycled A4 paper. The results are shown in Tables 11 to 13 below. The photoreceptor using the compound of this patent showed good images up to 100,000 times, but the photoreceptor using the comparative photoreceptor showed good images after 20,000 to 30,000 times. Several white spots appeared on the solid black part. The white spots were evaluated by visually counting the number of white spots generated on an A4 solid black image. The results are shown in Tables 18 to 20. (Evaluation Example 3) Using Digital Copy U-Bix8028 manufactured by Konica, it was tested at room temperature (25°C) and at low temperature (
10°C), unexposed part potential VH, exposed part potential V
L was measured. The results are shown in Tables 21 to 24 below. (Evaluation Example 4) The digital copy U-Bix8028 manufactured by Konica Corporation, which is the same as that used in Evaluation Example 3, was
The developer was loaded, images were produced several times, and black spots on the white background of the copied images were evaluated. The results are in Tables 25 to 28 below.
It was shown to. [0199] For evaluation of black spots, the particle size and number of black spots were measured using an image analysis device "Omnicon 300 Model" (manufactured by Shimadzu Corporation), and black spots with a diameter of 0.05 mm or more were determined. Judgment was made based on the number of pieces per cm2. The criteria for black spot evaluation are as shown in the table below. [0200] It should be noted that if the result of black spot determination is ◎ or ○, it will be practical, but
△ may not be suitable for practical use, and × may not be suitable for practical use. [0201] [0202] [0203] [0204] [0205] [0206] [0207] [0208] [0209] [0210] [0211] [0212] [0213] [0214] [0215] [0216] [0217] ] As described above, the electrophotographic photoreceptor according to the present invention When incorporated into a copying machine, printer, etc. and used repeatedly, it has high sensitivity and produces good images without image defects such as white spots, black spots, fogging, or loss of density. Furthermore, even when the electrophotographic photoreceptor according to the present invention is incorporated into a high-speed copying machine, printer, etc. and used repeatedly, the residual potential is small, and good images without image defects or poor image quality can be obtained. Next, Examples 71 to 140 and Comparative Example 15
-28 were evaluated in the same way as above, and the results shown in Tables 29 to 42 below were obtained. [0232] [0234] [0235] [0236] [0237] [0238] [0239] [0240] [0241] [0242] [0243] [0244] [0245] [0246] [0247] [0248] Example 141 Next, unlike the above example, An example in which the present invention is applied to EL (electroluminescence) will be described. [0261] On the transparent electrode (indium-tin oxide layer) formed on the glass substrate, a charge injection layer of 500%
Exemplified Compound 1 was deposited to a thickness of 60 Å, and then 8-quinolinol A1 complex (A1q3) was deposited as an organic fluorescent layer.
It was deposited to a thickness of 0 Å, and a magnesium/silver alloy was further deposited thereon as a negative electrode. [0262] When the light emission characteristics of the obtained organic thin film EL device were investigated, the light emission of 0.04 mW/cm2 was 4 mA/cm2.
Obtained in cm2. The emitted light color was yellow-green. [Formula 7] [Formula 7] [Formula 8] [Formula 1] [Formula 13] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Formula 21] [Formula 22] [Formula 22] [Formula 279] [Formula 23] [Formula 280] [Formula 24] [Formula 25] [Formula 25] [Formula 282] [Formula 26] [Formula 27] [Formula 27] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image 42] [Formula 43] [Formula 43] [Formula 44] [Formula 45] [Formula 45] [Formula 46] [Formula 46] [Formula 47] [Formula 47] [Formula 48] [Formula 49] embedded image embedded image [Formula 57] [Formula 57] [Formula 58] [Formula 59] [Formula 59] [Formula 61]

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum diagram of an example of a carrier transport material according to the present invention.

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

FIG. 7 is a sectional view of still another example of the 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 (4)

[Claims] [Claim 1] A bisstyryl compound represented by the following general formula [I]. [Chemical formula 1] {However, in this general formula [I], R1 has 1 carbon atom
-4 alkyl group, -OR2 (R2 has 1 carbon atom
~4 alkyl group), (R3, R4 are alkyl group, phenyl group, aralkyl group), halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, cyano group, phenyl group, aralkyl group, When ≧2, they may be different from each other. Ar
1, Ar2, Ar3, Ar4 are heterocyclic groups (R5
, R6, R7 are the same as R1, m≧2, n
When ≧2 and q≧2, they may be different from each other. ), and Ar1 and Ar2, Ar3 and Ar4 may each cooperate with each other to form a ring. is not the same as l≧1, m≧0, n≧0, and q≧0. } [Claim 2] A bisstyryl compound represented by the following general formula [II]. [Formula 2] {However, in this general formula [II], Ar1 , Ar2 ,
Ar3, Ar4 are heterocyclic groups (m=0 to 5, but Ar1, Ar2,
When all of Ar3 and Ar4 are, and three of them are m=0 and one of them is m=1, R5 is an alkyl group having 2 to 4 carbon atoms, -O
R2 (R2 is an alkyl group having 2 to 4 carbon atoms), (
R3, R4 are alkyl groups, phenyl groups, aralkyl groups), -CH2 COOR8 (R8 is an alkyl group)
, -OCOR9 (R9 is an alkyl group, a phenyl group,
aralkyl group), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, or an aralkyl group, and in other cases, R5 is a halogenated alkyl group having 1 to 4 carbon atoms.
-4 alkyl group, -OR10 (R10 has 1 carbon atom
~4 alkyl group), (R11 and R12 are an alkyl group, a phenyl group, an aralkyl group), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, an aralkyl group, and n= 0 to 7, q=0 to 7, and R6 and R7 are an alkyl group having 1 to 4 carbon atoms, -OR10 (R10
are the same as above), (R11 and R12 are the same as above), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, an aralkyl group, m≧2, n≧2, or q≧
2, multiple R5, multiple R6, multiple R7
may be different from each other. ), and Ar1 and Ar2, Ar3 and Ar4 may each cooperate with each other to form a ring. is not the same as } 3. An electrophotographic photoreceptor containing a bisstyryl compound represented by the following general formula [I]. [Chemical formula 3] {However, in this general formula [I], R1 has 1 carbon atom
-4 alkyl group, -OR2 (R2 has 1 carbon atom
~4 alkyl group), (R3, R4 are alkyl group, phenyl group, aralkyl group), halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, cyano group, phenyl group, aralkyl group, When ≧2, they may be different from each other. Ar
1, Ar2, Ar3, Ar4 are heterocyclic groups (R5
, R6, R7 are the same as R1, m≧2, n
When ≧2 and q≧2, they may be different from each other. ), and Ar1 and Ar2, Ar3 and Ar4 may each cooperate with each other to form a ring. is not the same as l≧1, m≧0, n≧0, and q≧0. } 4. An electrophotographic photoreceptor containing a bisstyryl compound represented by the following general formula [II]. embedded image {However, in this general formula [II], Ar1 , Ar2 ,
Ar3, Ar4 are heterocyclic groups (m=0 to 5, but Ar1, Ar2,
When all of Ar3 and Ar4 are m=0 for three of them and m=1 for one, R5 is an alkyl group having 2 to 4 carbon atoms, -OR2
(R2 is an alkyl group having 2 to 4 carbon atoms), (R3
, R4 is an alkyl group, phenyl group, aralkyl group)
, -CH2COOR8 (R8 is an alkyl group), -
OCOR9 (R9 is an alkyl group, a phenyl group, an aralkyl group), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, an aralkyl group; in other cases, R5 is a carbon atom Numbers 1-4
an alkyl group, -OR10 (R10 has 1 to 4 carbon atoms)
(R11, R12 are an alkyl group, a phenyl group, an aralkyl group), a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a cyano group, a phenyl group, an aralkyl group, and n=0 to 7, q=0 to 7, R6, R7
is an alkyl group having 1 to 4 carbon atoms, -OR10(R
10 is the same as above), (R11 and R12 are the same as above), halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, cyano group, phenyl group, aralkyl group, m≧2, n≧2 or q≧
2, multiple R5, multiple R6, multiple R7
may be different from each other. ), and Ar1 and Ar2, Ar3 and Ar4 may each cooperate with each other to form a ring. is not the same as }