JPH06116224A - Hydrazone compound and electrophotographic sensitizer using the same - Google Patents

Abstract

PURPOSE:To provide a new hydrazone compound capable of giving electrophotographic sensitizers having high sensitivity and excellent in repeated use characteristics, useful as an electric charge-transmitting material and excellent in chemical stability. CONSTITUTION:The objective compound of formula I (R<1> and R<3> are each alkyl or aryl; R<2> and R<4> are each arlyl; R<5>-R<8> are each H, alkyl, aryl or halogen; where at least one of them is not H) can be obtained be the following process: a reaction is carried out between an aldehyde compound of formula II and a compound of formula III in DMF mixed with t-butoxypotassium to produce a compound of formula IV, and vitride is dripped into THF mixed with the compound of the formula IV to carry out reaction, and the resultant compound of formula V is refluxed with a compound of formula VI in ethanol under heating. The electrophotographic sensitizer can be obtained by forming, on an electrically conductive substrate, a photosensitive layer comprising the compound of the formula I as an electric charge-transmitting material, electric charge-producing material and a binder resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel hydrazone compound and an electrophotographic photosensitive member using the same.

[0002]

2. Description of the Related Art The Carlson process is widely used to form a copied image using an electrophotographic photosensitive member. The Carlson process includes a charging step for uniformly charging a photoconductor by corona discharge, and an exposure step for exposing a charged image on a document image to form an electrostatic latent image corresponding to the document image on the photoconductor surface. A developing step of developing the electrostatic latent image with a developer containing toner to form a toner image, a transfer step of transferring the toner image to a base material such as paper, and a transfer step of transferring the toner image to the base material. And a cleaning step of removing the toner remaining on the photoconductor after the transfer step.

In order to form a high quality image in this Carlson process, it is required that the electrophotographic photosensitive member has excellent charging characteristics and photosensitive characteristics and that the residual potential after exposure is low.

Conventionally, a photoreceptor using an inorganic photoconductor such as selenium or cadmium sulfide as an electrophotographic photoreceptor material has been known, but these are not preferable because they are toxic and the production cost is high.

Therefore, so-called organic electrophotographic photoreceptors have been proposed in which, instead of these inorganic substances, various organic substances which are excellent in processability and economy and have a high degree of freedom in functional design are used. Such an organic electrophotographic photoreceptor usually has a photosensitive layer containing a charge generating material that generates a charge upon exposure and a charge transporting material that has a function of transporting the generated charge.

In order to satisfy various conditions required for such an organic electrophotographic photosensitive member, as a charge transporting material used in this type of photosensitive member, one having a high carrier mobility or chemical stability is used. Excellent things are required.

Conventionally, various organic compounds have been proposed as charge transport materials, and for example, the hydrazone compounds disclosed in Japanese Patent Laid-Open No. 4-4260 are known.

[0008]

However, the above-mentioned conventional charge-transporting materials do not yet have sufficient chemical stability, and therefore, the photoreceptors using these charge-transporting materials have poor sensitivity, Moreover, the repeatability is not sufficient. The reason is shown below. That is, at the time of preparation of the photosensitive layer coating liquid at the time of manufacturing the photosensitive member, impurities may inevitably be mixed in at present. Also, the photoconductor
When a copy image is formed, it is exposed to ozone and nitrogen oxides generated by corona discharge in the charging step and is exposed to light in the exposure step.

That is, the charge-transporting material having poor chemical stability is decomposed by the impurities in the photosensitive layer and ozone, nitrogen oxides, and light which are external attacking substances, and loses its charge-transporting ability. Or, it changes into a substance that becomes a deep trap that causes a reaction and hinders the electrophotographic characteristics.

The present invention has been made to solve the above-mentioned conventional drawbacks, and an object thereof is to provide a novel hydrazone compound having excellent chemical stability as a charge transport material. Further, another object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity and excellent repeating characteristics by containing the hydrazone compound.

[0011]

The hydrazone-based compound of the present invention is a hydrazone-based compound represented by the following general formula (1), by which the above object is achieved:

[0012]

[Chemical 2]

In the formula, R1 and R3 are the same or different and represent an alkyl group or an aryl group; R2 and R4 are an aryl group; R5 to R8 are the same or different and are a hydrogen atom, an alkyl group, It represents an aryl group or a halogen atom, and at least one of R5 to R8 is an alkyl group, an aryl group, or a halogen atom.

The electrophotographic photoreceptor of the present invention comprises a conductive substrate and a photosensitive layer formed on the conductive substrate, the photosensitive layer comprising a charge transport material, a charge generating material and a binder. The charge-transporting material containing a resin is a hydrazone compound represented by the general formula (1), and thereby the above-mentioned object is achieved.

[0015]

The hydrazone compound of the present invention is effective as a charge transport material, particularly a hole transport material, and has higher chemical stability than conventionally known charge transport materials such as hydrazone compounds.

That is, since the hydrazone compound of the present invention has a long π-electron conjugated system, it has an excellent hole transporting ability. Further, the central benzene ring has at least one substituent such as an alkyl group, an aryl group and a halogen atom, and due to the steric hindrance of these substituents,
The hydrazone compound is protected from attacks such as impurities that may be mixed in during preparation of the photosensitive layer, ozone and nitrogen oxides generated during charging, and light during exposure, and chemical stability is improved. That is, the hydrazone-based compound of the present invention exerts an inhibitory action against deterioration of being decomposed by the above-mentioned attack or changing into a substance that becomes a deep trap that causes a reaction and inhibits electrophotographic characteristics, a chemical It can be said that it has a stable structure. Furthermore, when R2 in the general formula (1) is a naphthyl group, a phenanthryl group or a pyrenyl group, the chemical stability is further improved by the quencher effect.

The hydrazone compound of the present invention can be used as a charge transport material for an electrophotographic photoreceptor as described above, and can also be used as a charge transport material for electronic devices such as organic solar cells and EL devices.

Since the electrophotographic photosensitive member of the present invention has the photosensitive layer containing the hydrazone compound, it has high sensitivity and excellent durability.

[0019]

Preferred embodiments of the alkyl group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group,
Hexyl group and the like can be mentioned.

Examples of the aryl group include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group and pyrenyl group. These may have a substituent.

Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and fluorine atom.

Among the hydrazone compounds represented by the above general formula (1), the following general formulas (2), (3), and (3) have a structure in which the formed π-electron conjugated system is more chemically stable.
A hydrazone compound represented by (4) is shown.

[0023]

[Chemical 3]

In the formula, R1 and R3 are the same or different and each represents an alkyl group or an aryl group; R4 represents an aryl group; R9 represents an alkyl group, an aryl group or a halogen atom.

[0025]

[Chemical 4]

In the formula, R1 and R3 are the same or different and each represents an alkyl group or an aryl group; R4 represents an aryl group; R9 represents an alkyl group, an aryl group or a halogen atom.

[0027]

[Chemical 5]

In the formula, R1 and R3 are the same or different and each represent an alkyl group or an aryl group; R4 represents an aryl group; R9 represents an alkyl group, an aryl group or a halogen atom.

Specific examples of the hydrazone compound represented by the above general formula (1) include compounds in which R1 to R8 in the formula (1) have the following substituents.

1. Compound 1 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 1. Compound 2 R1 = methyl group, R2-R5 = phenyl group, R6-R8
= Hydrogen atom 3. Compound 3 R1 to R5 = phenyl group, R6 to R8 = hydrogen atom 4. Compound 4 R1 = ethyl group, R2 = phenyl group, R3 = ethyl group,
R4, R5 = phenyl group, R6 to R8 = hydrogen atom 5. Compound 5 R1 = methyl group, R2 = phenyl group, R3 = ethyl group,
R4, R5 = phenyl group, R6 to R8 = hydrogen atom 6. Compound 6 R1 to R4 = orthotolyl group, R5 = phenyl group, R6
~ R8 = hydrogen atom 7. Compound 7 R1 to R4 = metatryl group, R5 = phenyl group, R6 to
R8 = hydrogen atom 8. Compound 8 R1 to R4 = paratolyl group, R5 = phenyl group, R6 to
R8 = hydrogen atom 9. Compound 9 R1, R3 = metatryl group, R2, R4 = paratolyl group, R5 = phenyl group R6 to R8 = hydrogen atom 10. Compound 10 R1 to R4 = metachloro-phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 11. Compound 11 R1 to R4 = metabromo-phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 12. Compound 12 R1 to R4 = metaethyl-phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 13. Compound 13 R1 to R4 = metatrifluoromethyl-phenyl group, R
5 = phenyl group, R6 to R8 = hydrogen atom 14. Compound 14 R1 to R4 = metamethoxy-phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 15. Compound 15 R1 = trifluoromethyl group, R2 = phenyl group, R3
= Trifluoromethyl group, R4 = phenyl group, R5 = phenyl group, R6 to R8 = hydrogen atom 16. Compound 16 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 to R6 = phenyl group, R7, R8 = hydrogen atom 17. Compound 17 R1 to R6 = phenyl group, R7, R8 = hydrogen atom 18. Compound 18 R1 to R4 = metatryl group, R5, R6 = phenyl group,
R7, R8 = hydrogen atom 19. Compound 19 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = phenyl group, R6 = hydrogen atom, R7 = phenyl group, R8 = hydrogen atom 20. Compound 20 R1 to R5 = phenyl group, R6 = hydrogen atom, R7 = phenyl group, R8 = hydrogen atom 21. Compound 21 R1 to R4 = metatryl group, R5 = phenyl group, R6 =
Hydrogen atom, R7 = phenyl group, R8 = hydrogen atom 22. Compound 22 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4, R5 = phenyl group, R6 = hydrogen atom, R7 = methyl group, R8 = hydrogen atom 23. Compound 23 R1 to R5 = phenyl group, R6 = hydrogen atom, R7 = methyl group, R8 = hydrogen atom 24. Compound 24 R1 to R4 = metatryl group, R5 = phenyl group, R6 =
Hydrogen atom, R7 = methyl group, R8 = hydrogen atom 25. Compound 25 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = methyl group, R6 = hydrogen atom, R7 = methyl group, R
8 = hydrogen atom 26. Compound 26 R1 to R4 = phenyl group, R5 = methyl group, R6 = hydrogen atom, R7 = methyl group, R8 = hydrogen atom 27. Compound 27 R1 to R4 = metatryl group, R5 = methyl group, R6 = hydrogen atom, R7 = methyl group, R8 = hydrogen atom 28. Compound 28 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4, R5 = phenyl group, R6 = methyl group, R7 = phenyl group, R8 = methyl group 29. Compound 29 R1 to R5 = phenyl group, R6 = methyl group, R7 = phenyl group, R8 = methyl group 30. Compound 30 R1 to R4 = metatryl group, R5 = phenyl group, R6 =
Methyl group, R7 = phenyl group, R8 = methyl group 31. Compound 31 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = chlorine atom, R6 to R8 = hydrogen atom 32. Compound 32 R1 to R4 = phenyl group, R5 = chlorine atom, R6 to R8
= Hydrogen atom 33. Compound 33 R1 to R4 = metatryl group, R5 = chlorine atom, R6 to R
8 = hydrogen atom 34. Compound 34 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = chlorine atom, R6 = hydrogen atom, R7 = chlorine atom, R
8 = hydrogen atom 35. Compound 35 R1 to R4 = phenyl group, R5 = chlorine atom, R6 = hydrogen atom, R7 = chlorine atom, R8 = hydrogen atom 36. Compound 36 R1 to R4 = metatryl group, R5 = chlorine atom, R6 = hydrogen atom, R7 = chlorine atom, R8 = hydrogen atom 37. Compound 37 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = bromine atom, R6-R8 = hydrogen atom 38. Compound 38 R1 to R4 = phenyl group, R5 = bromine atom, R6 to R8
= Hydrogen atom 39. Compound 39 R1 to R4 = metatryl group, R5 = bromine atom, R6 to R
8 = Hydrogen atom Specific examples of the hydrazone compound represented by the above general formula (2) include compounds in which R1, R3, R4 and R9 in the formula (2) have the following substituents.

40. Compound 40 R1, R3 = methyl group, R4 = phenyl group, R9 = hydrogen atom 41. Compound 41 R1 = methyl group, R3, R4 = phenyl group, R9 = hydrogen atom 42. Compound 42 R1, R3, R4 = phenyl group, R9 = hydrogen atom 43. Compound 43 R1, R3 = methyl group, R4 = naphthyl group, R9 = hydrogen atom 44. Compound 44 R1 = methyl group, R3, R4 = naphthyl group, R9 = hydrogen atom 45. Compound 45 R1, R3, R4 = naphthyl group, R9 = hydrogen atom 46. Compound 46 R1, R3 = ethyl group, R4 = phenyl group, R9 = hydrogen atom 47. Compound 47 R1, R3 = ethyl group, R4 = naphthyl group, R9 = hydrogen atom 48. Compound 48 R1, R3 = phenyl group, R4 = naphthyl group, R9 = hydrogen atom 49. Compound 49 R1 = methyl group, R3 = ethyl group, R4 = phenyl group,
R9 = hydrogen atom 50. Compound 50 R1, R3, R4 = orthotolyl group, R9 = hydrogen atom 51. Compound 51 R1, R3, R4 = metatryl group, R9 = hydrogen atom 52. Compound 52 R1, R3, R4 = paratolyl group, R9 = hydrogen atom 53. Compound 53 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 54. Compound 54 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 55. Compound 55 R1, R3 = paratolyl group, R4 = naphthyl group, R9 =
Hydrogen atom 56. Compound 56 R1, R3, R4 = metachloro-phenyl group, R9 = hydrogen atom 57. Compound 57 R1, R3, R4 = metabromo-phenyl group, R9 = hydrogen atom 58. Compound 58 R1, R3, R4 = metaethyl-phenyl group, R9 = hydrogen atom 59. Compound 59 R1, R3, R4 = metatrifluoromethyl-phenyl group, R9 = hydrogen atom 60. Compound 60 R1, R3, R4 = metamethoxy-phenyl group, R9 =
Hydrogen atom 61. Compound 61 R1, R3, R4 = metatryl group, R9 = methyl group 62. Compound 62 R1, R3, R4 = metatryl group, R9 = ethyl group 63. Compound 63 R1, R3, R4 = metatryl group, R9 = phenyl group 64. Compound 64 R1, R3, R4 = metatryl group, R9 = chlorine atom 65. Compound 65 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Methyl group 66. Compound 66 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Ethyl group 67. Compound 67 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Phenyl group 68. Compound 68 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Chlorine atom 69. Compound 69 R1, R3, R4 = naphthyl group, R9 = methyl group 70. Compound 70 R1, R3, R4 = naphthyl group, R9 = ethyl group 71. Compound 71 R1, R3, R4 = naphthyl group, R9 = phenyl group 72. Compound 72 R1, R3, R4 = naphthyl group, R9 = chlorine atom 73. Compound 73 R1, R3 = methyl group, R4 = phenyl group, R9 = methyl group 74. Compound 74 R1, R3 = methyl group, R4 = phenyl group, R9 = ethyl group 75. Compound 75 R1, R3 = methyl group, R4 = phenyl group, R9 = phenyl group 76. Compound 76 R1, R3 = methyl group, R4 = phenyl group, R9 = chlorine atom As specific examples of the hydrazone compound represented by the general formula (3), R1, R3, R4 and R9 in the formula (3) are: The compound which has the following substituents is mentioned.

77. Compound 77 R1, R3 = methyl group, R4 = phenyl group, R9 = hydrogen atom 78. Compound 78 R1 = methyl group, R3, R4 = phenyl group, R9 = hydrogen atom 79. Compound 79 R1, R3, R4 = phenyl group, R9 = hydrogen atom 80. Compound 80 R1, R3 = methyl group, R4 = naphthyl group, R9 = hydrogen atom 81. Compound 81 R1 = methyl group, R3, R4 = naphthyl group, R9 = hydrogen atom 82. Compound 82 R1, R3, R4 = naphthyl group, R9 = hydrogen atom 83. Compound 83 R1, R3 = ethyl group, R4 = phenyl group, R9 = hydrogen atom 84. Compound 84 R1, R3 = ethyl group, R4 = naphthyl group, R9 = hydrogen atom 85. Compound 85 R1, R3 = phenyl group, R4 = naphthyl group, R9 = hydrogen atom 86. Compound 86 R1 = methyl group, R3 = ethyl group, R4 = phenyl group,
R9 = hydrogen atom 87. Compound 87 R1, R3, R4 = orthotolyl group, R9 = hydrogen atom 88. Compound 88 R1, R3, R4 = metatryl group, R9 = hydrogen atom 89. Compound 89 R1, R3, R4 = paratolyl group, R9 = hydrogen atom 90. Compound 90 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 91. Compound 91 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 92. Compound 92 R1, R3 = paratolyl group, R4 = naphthyl group, R9 =
Hydrogen atom 93. Compound 93 R1, R3, R4 = metachloro-phenyl group, R9 = hydrogen atom 94. Compound 94 R1, R3, R4 = metabromo-phenyl group, R9 = hydrogen atom 95. Compound 95 R1, R3, R4 = metaethyl-phenyl group, R9 = hydrogen atom 96. Compound 96 R1, R3, R4 = metatrifluoromethyl-phenyl group, R9 = hydrogen atom 97. Compound 97 R1, R3, R4 = metamethoxy-phenyl group, R9 =
Hydrogen atom 98. Compound 98 R1, R3, R4 = metatryl group, R9 = methyl group 99. Compound 99 R1, R3, R4 = metatryl group, R9 = ethyl group 100. Compound 100 R1, R3, R4 = metatryl group, R9 = phenyl group 101. Compound 101 R1, R3, R4 = metatryl group, R9 = chlorine atom 102. Compound 102 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Methyl group 103. Compound 103 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Ethyl group 104. Compound 104 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Phenyl group 105. Compound 105 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Chlorine atom 106. Compound 106 R1, R3, R4 = naphthyl group, R9 = methyl group 107. Compound 107 R1, R3, R4 = naphthyl group, R9 = ethyl group 108. Compound 108 R1, R3, R4 = naphthyl group, R9 = phenyl group 109. Compound 109 R1, R3, R4 = naphthyl group, R9 = chlorine atom 110. Compound 110 R1, R3 = methyl group, R4 = phenyl group, R9 = methyl group 111. Compound 111 R1, R3 = methyl group, R4 = phenyl group, R9 = ethyl group 112. Compound 112 R1, R3 = methyl group, R4 = phenyl group, R9 = phenyl group 113. Compound 113 R1, R3 = methyl group, R4 = phenyl group, R9 = chlorine atom As specific examples of the hydrazone compound represented by the general formula (4), R1, R3, R4 and R9 in the formula (4) are: The compound which has the following substituents is mentioned.

114. Compound 114 R1, R3 = methyl group, R4 = phenyl group, R9 = hydrogen atom 115. Compound 115 R1 = methyl group, R3, R4 = phenyl group, R9 = hydrogen atom 116. Compound 116 R1, R3, R4 = phenyl group, R9 = hydrogen atom 117. Compound 117 R1, R3 = methyl group, R4 = naphthyl group, R9 = hydrogen atom 118. Compound 118 R1 = methyl group, R3, R4 = naphthyl group, R9 = hydrogen atom 119. Compound 119 R1, R3, R4 = naphthyl group, R9 = hydrogen atom 120. Compound 120 R1, R3 = ethyl group, R4 = phenyl group, R9 = hydrogen atom 121. Compound 121 R1, R3 = ethyl group, R4 = naphthyl group, R9 = hydrogen atom 122. Compound 122 R1, R3 = phenyl group, R4 = naphthyl group, R9 = hydrogen atom 123. Compound 123 R1 = methyl group, R3 = ethyl group, R4 = phenyl group,
R9 = hydrogen atom 124. Compound 124 R1, R3, R4 = orthotolyl group, R9 = hydrogen atom 125. Compound 125 R1, R3, R4 = metatryl group, R9 = hydrogen atom 126. Compound 126 R1, R3, R4 = paratolyl group, R9 = hydrogen atom 127. Compound 127 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 128. Compound 128 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Hydrogen atom 129. Compound 129 R1, R3 = paratolyl group, R4 = naphthyl group, R9 =
Hydrogen atom 130. Compound 130 R1, R3, R4 = metachloro-phenyl group, R9 = hydrogen atom 131. Compound 131 R1, R3, R4 = metabromo-phenyl group, R9 = hydrogen atom 132. Compound 132 R1, R3, R4 = metaethyl-phenyl group, R9 = hydrogen atom 133. Compound 133 R1, R3, R4 = metatrifluoromethyl-phenyl group, R9 = hydrogen atom 134. Compound 134 R1, R3, R4 = metamethoxy-phenyl group, R9 =
Hydrogen atom 135. Compound 135 R1, R3, R4 = methatryl group, R9 = methyl group 136. Compound 136 R1, R3, R4 = metatryl group, R9 = ethyl group 137. Compound 137 R1, R3, R4 = metatryl group, R9 = phenyl group 138. Compound 138 R1, R3, R4 = metatryl group, R9 = chlorine atom 139. Compound 139 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Methyl group 140. Compound 140 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Ethyl group 141. Compound 141 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Phenyl group 142. Compound 142 R1, R3 = metatryl group, R4 = naphthyl group, R9 =
Chlorine atom 143. Compound 143 R1, R3, R4 = naphthyl group, R9 = methyl group 144. Compound 144 R1, R3, R4 = naphthyl group, R9 = ethyl group 145. Compound 145 R1, R3, R4 = naphthyl group, R9 = phenyl group 146. Compound 146 R1, R3, R4 = naphthyl group, R9 = chlorine atom 147. Compound 147 R1, R3 = methyl group, R4 = phenyl group, R9 = methyl group 148. Compound 148 R1, R3 = methyl group, R4 = phenyl group, R9 = ethyl group 149. Compound 149 R1, R3 = methyl group, R4 = phenyl group, R9 = phenyl group 150. Compound 150 R1, R3 = methyl group, R4 = phenyl group, R9 = chlorine atom The hydrazone compound of the present invention represented by the above general formula (1) can be synthesized, for example, as follows.

First, in DMF mixed with tertiary-butoxy potassium, the aldehyde compound represented by the formula (a) and the compound represented by the formula (b) are reacted to form the compound represented by the formula (c). To obtain the compound.

[0035]

[Chemical 6]

[0036]

[Chemical 7]

[0037]

[Chemical 8]

In the formula, R1 represents an alkyl group or an aryl group; R2 represents an aryl group; R5 to R8 represent
The same or different, each represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and at least one of R5 to R8 is an alkyl group, an aryl group, or a halogen atom.

Next, vitrid is added dropwise to tetrahydrofuran mixed with the compound represented by the formula (c) and reacted to obtain a compound represented by the formula (d).

[0040]

[Chemical 9]

Then, the compound represented by the formula (d) and the compound represented by the formula (e) are heated to reflux in ethanol to give the hydrazone compound represented by the general formula (1). obtain.

[0042]

[Chemical 10]

In the formula, R3 represents an alkyl group or an aryl group, and R4 represents an aryl group.

The electrophotographic photosensitive member of the present invention may have a single photosensitive layer or a laminated layer composed of a plurality of functionally separated layers.

When the photosensitive layer is a single layer, the photosensitive layer has a photosensitive layer formed on a conductive substrate. This photosensitive layer contains the hydrazone compound of the present invention as a charge transporting material, a charge generating material, and a binder resin in the same layer.

When the photosensitive layer is a function-separated type laminate,
The photoconductor is formed by forming a charge generation layer on a conductive substrate and further stacking a charge transport layer on the charge generation layer. The charge generation layer is formed by vapor deposition or by dispersing the charge generation material in a suitable binder resin and applying the coating material. The charge transport layer contains a charge transport material and a binder resin. Alternatively, the photoreceptor may have the charge generation layer and the charge transport layer formed in reverse order.

In the case of a single-layer type photosensitive layer, the photosensitive layer contains 2 to 20 parts of the charge generating material per 100 parts by weight of the binder resin.
It is contained in an amount of 3 parts by weight, preferably 3 to 15 parts by weight. Further, this photosensitive layer contains 40 to 200 parts by weight, and preferably 50 to 150 parts by weight of the charge transport material of the present invention with respect to 100 parts by weight of the binder resin.

On the other hand, in the case of the laminated type photosensitive layer, the charge generating material and the binder resin may be contained in various ratios. Generally, 5 parts of the charge generation material is added to 100 parts by weight of the binder resin.
To 500 parts by weight, preferably 10 to 250 parts by weight. Further, the photosensitive layer may contain the charge transport material and the binder resin in various ratios. In order to easily transport the charges generated in the charge generation layer by light irradiation, 10 to 10 parts by weight of the charge transport material of the present invention is used with respect to 100 parts by weight of the binder resin.
It is contained in an amount of 500 parts by weight, preferably 25 to 200 parts by weight.

The thickness of the photosensitive layer is 10 in the case of a single layer type.
˜50 μm, preferably 15˜30 μm.
On the other hand, in the case of the laminated type, the thickness of the charge generation layer may have any film thickness, but is generally 0.01 to 5 μm, and more preferably about 0.1 to 3 μm. On the other hand, the thickness of the charge transport layer is generally 2 to 100 μm, preferably about 5 to 50 μm.

The constituent materials of the electrophotographic photosensitive member of the present invention will be described below.

(Conductive Substrate) As the above-mentioned conductive substrate,
For example, metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, iodide Examples thereof include glass coated with aluminum, tin oxide, indium oxide and the like.

The conductive substrate may be in the form of a sheet, a drum, or the like, as long as the base material itself has conductivity or the surface of the base material has conductivity. This substrate preferably has sufficient mechanical strength when used.

(Charge Generating Material) The charge generating material is selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, azo compounds, disazo compounds, phthalocyanine compounds, ansanthrone compounds which have been conventionally used. Compounds, perylene compounds, indigo compounds, triphenylmethane compounds, slene compounds,
Examples thereof include toluidine compounds, pyrazoline compounds, quinacridone compounds, and pyrrolopyrrole compounds. These charge generating materials are used alone or in combination of two or more.

(Charge Transport Material) As the charge transport material, the novel hydrazone compound of the present invention is used alone or in combination of two or more. Alternatively, the novel hydrazone compounds of the present invention may be used in combination with other conventionally known charge transport materials. Conventionally known charge transport materials include, for example, 2,5-di (4-methylaminophenyl) -1,3.
Oxadiazole compounds such as 4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline Nitrogen-containing cyclic compounds such as pyrazoline compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds, etc. Compounds and fused polycyclic compounds are mentioned. The binder resin is not always necessary when using a charge transporting material having film-forming properties such as polyvinylcarbazole.

(Binder Resin) As the binder resin, various resins can be used. For example, styrene polymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer Combined, chlorinated polyethylene, polyvinyl chloride, polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether Examples thereof include thermoplastic resins such as resins; silicone resins, epoxy resins, and other crosslinkable thermosetting resins; and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins are used alone or in combination of two or more.

(Sensitizer and Other Additives) In order to enhance the sensitivity of the charge generating layer, known sensitizers such as terphenyl, halonaphthoquinones and acenaphthylene may be used together with the charge generating material. .

Furthermore, in order to improve the dispersibility and coatability of the charge transport material and the charge generating material, a surfactant,
A leveling agent or the like may be used.

(Organic Solvent) As will be described later, a solvent is used when a charge generating material, a charge transporting material, and a binder resin are dissolved to prepare a coating solution. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol and butanol; aliphatic hydrocarbons such as n-hexane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; dichloromethane, dichloroethane, Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone; ethyl acetate,
Esters such as methyl acetate; dimethylformaldehyde, dimethylformamide, dimethylsulfoxide and the like can be mentioned. These solvents may be used alone or in combination of two or more.

(Film Forming) When the photosensitive layer having the charge generating layer and the charge transporting layer is formed by a coating means, the charge generating material or the charge transporting material and the binder resin are formed by a conventionally known method, for example, A coating solution is prepared using a roll mill, a ball mill, an attritor, a paint shaker, an ultrasonic disperser, or the like.

[0060]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples.

Example 1 <Synthesis of Compound 2>

[0062]

[Chemical 11]

(1) Tertiary-butoxy potassium 20
In 300 ml of DMF mixed with g, 20.72 g (100 mmol) of the compound represented by the following formula (A1) and 24.23 g (100 mmo of the compound represented by the following formula (B1).
1) and were added and reacted at 80 ° C. for 5 hours with stirring.

[0064]

[Chemical 12]

[0065]

[Chemical 13]

Next, the obtained reaction product is poured into water, filtered, washed with water, and further washed with ethanol, and dried to give a compound 16.6 of a white crystal represented by the following formula (C1).
9 g was obtained. The yield was 56.5%.

[0067]

[Chemical 14]

(2) Compound (C1) 5.9 obtained above
1 g (20 mmol) of tetrahydrofuran 100 ml
Dissolved in. Vitrid (sodium bis (2-methoxy) aluminum hydride) was added to the resulting solution.
2.88 g (10.0 mmol) of 70% toluene solution of
Was added dropwise for 10 minutes while cooling to 5 ° C. This was stirred as it was at 5 ° C. for 5 hours, and then 30% H ₂ SO ₄ 100
ml was added dropwise, and the mixture was reacted for 15 hours with stirring.
The obtained reaction product was neutralized with a 40% NaOH aqueous solution and extracted with benzene to obtain 3.33 g of a pale yellow crystalline compound represented by the following formula (D1). Yield 53.3
%Met.

[0069]

[Chemical 15]

(3) Compound (D1) 3.1 obtained above
2 g (10 mmol) and 2.21 g (10 mmol) of the compound represented by the following formula (E1) were added to 100 ml of ethanol.
A small amount of acetic acid was added under reflux, and heating under reflux was continued for 3 hours.

[0071]

[Chemical 16]

After the reaction, water was added, the precipitate was filtered and n-
By washing with hexane, 2.04 g of a pale yellow crystalline compound represented by Compound 2 was obtained. Yield 43.8
%Met.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 465 Elemental analysis value: C ₃₄ H ₂₈ N ₂ , theoretical value (%): C = 87.90 H = 6.07 N =
6.03 measurement value (%): C = 87.99 H = 5.99 N =
5.92 (Example 2) <Synthesis of Compound 6>

[0075]

[Chemical 17]

(1) Instead of the compound represented by the above formula (B1), 26.03 g (1 of the compound represented by the following formula (F1)
00 mmol) and the reaction time was 4 instead of 5 hours.
Compound (15) of pale yellow crystal represented by the following formula (G1) according to the method of (1) of Example 1 except that the time was set.
30 g was obtained. The yield was 48.8%.

[0077]

[Chemical 18]

[0078]

[Chemical 19]

(2) 6.27 g (20) of the compound represented by the above formula (G1) instead of the compound represented by the above formula (C1)
(14 mmol) was used according to the method of (2) of Example 1 to obtain 4.14 g of a pale yellow crystalline compound represented by the following formula (H1). The yield was 62.7%.

[0080]

[Chemical 20]

(3) In place of the compound represented by the above formula (D1), 3.30 g (10) of the compound represented by the above formula (H1)
mmol), and instead of the compound represented by the above formula (E1), 12.48 g (1
0 mmol) was used according to the method of (3) of Example 1 to obtain 2.25 g of a yellow crystalline compound represented by the compound 6. The yield was 51.4%.

[0082]

[Chemical 21]

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 559 Elemental analysis value: C ₄₁ H ₃₈ N ₂ , theoretical value (%): C = 88.13 H = 6.85 N =
5.01 Measured value (%): C = 88.24 H = 6.90 N =
5.13 (Example 3) <Synthesis of Compound 18>

[0085]

[Chemical formula 22]

(1) Instead of the compound represented by the above formula (A1), 28.3 g (10) of the compound represented by the following formula (J1)
0 mmol), and instead of the compound represented by the above formula (B1), 26.3 g (1 of the compound represented by the following formula (K1)
00 mmol) and the reaction conditions were 100 ° C. for 6 hours instead of 80 ° C. for 5 hours, according to the method of (1) of Example 1, and represented by the following formula (L1). 15.08 g of a yellow crystalline compound was obtained. The yield was 38.7%.

[0087]

[Chemical formula 23]

[0088]

[Chemical formula 24]

[0089]

[Chemical 25]

(2) 7.79 g (20) of the compound represented by the above formula (L1) instead of the compound represented by the above formula (C1)
(7 mmol) was used according to the method of (2) of Example 1 to obtain 5.07 g of a pale yellow crystalline compound represented by the following formula (M1). The yield was 62.4%.

[0091]

[Chemical formula 26]

(3) Instead of the compound represented by the above formula (D1), 4.07 g (10) of the compound represented by the above formula (M1)
mmol) in place of the compound represented by the above formula (E1), 2.48 g (10) of the compound represented by the following formula (N1)
(19 mmol) was used according to the method of (3) of Example 1 to give 2.19 g of a yellow crystalline compound represented by the compound 18. The yield was 42.6%.

[0093]

[Chemical 27]

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 659 Elemental analysis value: C ₄₉ H ₄₂ N ₂ , theoretical value (%): C = 89.32 H = 6.43 N =
4.25 Measured value (%): C = 89.16 H = 6.46 N =
4.33 (Example 4) <Synthesis of Compound 21>

[0096]

[Chemical 28]

(1) Instead of the compound represented by the above formula (A1), 28.3 g (10) of the compound represented by the following formula (O1)
0 mmol), and instead of the compound represented by the above formula (B1), 26.3 g (1
00 mmol) and the reaction conditions were 90 ° C. for 4 hours instead of 80 ° C. for 5 hours, according to the method of (1) of Example 1, and represented by the following formula (P1). 14.18 g of a yellow crystalline compound was obtained. The yield was 36.4%.

[0098]

[Chemical 29]

[0099]

[Chemical 30]

(2) 7.79 g (20) of the compound represented by the above formula (P1) instead of the compound represented by the above formula (C1)
(28 mmol) was used according to the method of (2) of Example 1 to obtain 4.28 g of a pale yellow crystalline compound represented by the following formula (Q1). The yield was 52.6%.

[0101]

[Chemical 31]

(3) Instead of the compound represented by the above formula (D1), 4.07 g (10) of the compound represented by the above formula (Q1)
(15 mmol) was used according to the method of (3) of Example 1 to obtain 3.15 g of a yellow crystalline compound represented by the compound 21. The yield was 61.1%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 659 Elemental analysis value: C ₄₉ H ₄₂ N ₂ , theoretical value (%): C = 89.32 H = 6.43 N =
4.25 Measured value (%): C = 89.15 H = 6.40 N =
4.10 (Example 5) <Synthesis of Compound 26>

[0105]

[Chemical 32]

(1) 15.2 g (10) of a compound represented by the following formula (R1) instead of the compound represented by the above formula (A1)
0 mmol), and instead of the compound represented by the above formula (B1), 30.43 g of the compound represented by the following formula (S1)
18.07 g of a pale yellow crystalline compound represented by the following formula (T1) was obtained according to the method of (1) of Example 1 except that (100 mmol) was used. The yield was 58.4%.

[0107]

[Chemical 33]

[0108]

[Chemical 34]

[0109]

[Chemical 35]

(2) 6.19 g (20) of the compound represented by the above formula (T1) instead of the compound represented by the above formula (C1)
(34 mmol) was used according to the method of (2) of Example 1 to obtain 3.34 g of a pale yellow crystalline compound represented by the following formula (U1). The yield was 51.2%.

[0111]

[Chemical 36]

(3) In place of the compound represented by the above formula (D1), 3.26 g (10) of the compound represented by the above formula (U1)
2.05 g of a yellow crystalline compound represented by Compound 26 was obtained according to the method of (3) of Example 1 except that (mmol) was used. The yield was 42.8%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 479 Elemental analysis value: C ₃₅ H ₃₀ N ₂ , theoretical value (%): C = 87.83 H = 6.32 N =
5.85 Measured value (%): C = 87.73 H = 6.31 N =
5.72 (Example 6) <Synthesis of Compound 30>

[0115]

[Chemical 37]

(1) Instead of the compound represented by the above formula (A1), 31.14 g (1 of the compound represented by the following formula (V1)
00 mmol) and instead of the compound represented by the above formula (B1), 26.3 g of the compound represented by the above formula (K1)
(100 mmol) was used, and the reaction condition was changed to 120 ° C. for 6 hours instead of 80 ° C. for 5 hours, which is represented by the following formula (W1) according to the method of (1) of Example 1. 13.26 g of a pale yellow crystalline compound was obtained. Yield 27.2
%Met.

[0117]

[Chemical 38]

[0118]

[Chemical Formula 39]

(2) Instead of the compound represented by the above formula (C1), 9.75 g (20) of the compound represented by the above formula (W1)
(17 mmol) was used according to the method of (2) of Example 1 to obtain 5.17 g of a pale yellow crystalline compound represented by the following formula (X1). The yield was 51.2%.

[0120]

[Chemical 40]

(3) 5.05 g (10) of the compound represented by the above formula (X1) instead of the compound represented by the above formula (D1)
mmol) in place of the compound represented by the above formula (E1), 2.48 g (10) of the compound represented by the above formula (N1)
(43 mmol) was used, and according to the method of (3) of Example 1, 2.43 g of a compound of yellow crystals represented by Compound 30 was obtained. The yield was 35.4%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 687 Elemental analysis value: C ₅₁ H ₄₆ N ₂ , theoretical value (%): C = 89.17 H = 6.75 N =
4.08 measurement value (%): C = 89.02 H = 6.66 N =
4.03 (Example 7) <Synthesis of Compound 34>

[0124]

[Chemical 41]

(1) Instead of the compound represented by the above formula (A1), 20.00 g (1
00 mmol) and the reaction conditions were 90 ° C. for 7 hours instead of 80 ° C. for 5 hours, and the white color represented by the following formula (Z1) was used according to the method of (1) of Example 1. 28.88 g of crystalline compound are obtained. The yield was 54.1%.

[0126]

[Chemical 42]

[0127]

[Chemical 43]

(2) 5.78 g (20) of the compound represented by the above formula (Z1) instead of the compound represented by the above formula (C1)
(44 mmol) was used according to the method of (2) of Example 1 to obtain 3.44 g of a pale yellow crystalline compound represented by the following formula (A2). The yield was 56.4%.

[0129]

[Chemical 44]

(3) 3.05 g (10) of the compound represented by the above formula (A2) instead of the compound represented by the above formula (D1).
mmol), and instead of the compound represented by the above formula (E1), 1.59 g (10) of the compound represented by the following formula (B2).
(1.3 mmol) was used according to the method of Example 1 (3) except that (1.3 mmol) was used to obtain 1.39 g of a compound of light yellow crystals represented by compound 34. The yield was 35.1%.

[0131]

[Chemical formula 45]

The mass spectrum and elemental analysis values of this compound are as follows.

[0133] Mass spectrum: 394.395 Elementary analysis: as _{C 23 H 20 N 2 Cl 2} , the theoretical value (%): C = 69.91 H = 5.10 N =
7.09 measured value (%): C = 69.82 H = 4.96 N =
6.92 (Example 8) <Synthesis of Compound 51>

[0134]

[Chemical formula 46]

(1) In place of the compound represented by the above formula (A1), 13.14 g (1 of the compound represented by the following formula (C2)
00 mmol) and instead of the compound represented by the above formula (B1), 36.84 g of a compound represented by the following formula (D2)
(100 mmol) was used, and according to the method of (1) of Example 1 except that the reaction temperature was 100 ° C. instead of 80 ° C., the compound 162 of pale yellow crystal represented by the following formula (E2) was obtained. 0.36 g was obtained. The yield was 47.0%.

[0136]

[Chemical 47]

[0137]

[Chemical 48]

[0138]

[Chemical 49]

(2) 6.90 g (20) of the compound represented by the above formula (E2) instead of the compound represented by the above formula (C1)
(76 mmol) was used according to the method of (2) of Example 1 to obtain 3.76 g of a pale yellow crystalline compound represented by the following formula (F2). The yield was 52.0%.

[0140]

[Chemical 50]

(3) 3.62 g (10) of the compound represented by the above formula (F2) instead of the compound represented by the above formula (D1)
mmol) in place of the compound represented by the above formula (E1), 2.48 g (10) of the compound represented by the above formula (N1)
was used according to the method of (3) of Example 1 except that 2.13 g of a yellow crystal compound represented by the compound 51 was obtained. The yield was 45.3%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 471 Elemental analysis value: C ₃₄ H ₃₄ N ₂ , theoretical value (%): C = 86.77 H = 7.28 N =
5.95 Measured value (%): C = 86.85 H = 7.36 N =
6.09 (Example 9) <Synthesis of Compound 55>

[0144]

[Chemical 51]

(1) In place of the compound represented by the above formula (A1), 13.14 g (1 of the compound represented by the above formula (C2)
00 mmol), and instead of the compound represented by the above formula (B1), 36.84 g of a compound represented by the following formula (G2)
(100 mmol) was used, and according to the method of (1) of Example 1, except that the reaction time was 6 hours instead of 5 hours, the compound 1 of pale yellow crystal represented by the following formula (H2)
7.99 g was obtained. The yield was 52.1%.

[0146]

[Chemical 52]

[0147]

[Chemical 53]

(2) 6.90 g (20) of the compound represented by the above formula (H2) instead of the compound represented by the above formula (C1)
was used in the same manner as in (2) of Example 1 to obtain 3.88 g of a pale yellow crystalline compound represented by the following formula (I2). The yield was 53.6%.

[0149]

[Chemical 54]

(3) Instead of the compound represented by the above formula (D1), 3.62 g (10) of the compound represented by the above formula (I2)
mmol) in place of the compound represented by the above formula (E1), 2.84 g (10) of the compound represented by the following formula (J2)
2.55 g of a yellow crystalline compound represented by the compound 55 was obtained according to the method of (3) of Example 1 except that (mmol) was used. The yield was 44.0%.

[0151]

[Chemical 55]

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 579 Elemental analysis value: C ₄₃ H ₃₄ N ₂ , theoretical value (%): C = 89.24 H = 5.92 N =
4.84 Measured value (%): C = 89.18 H = 6.06 N =
4.71 (Example 10) <Synthesis of Compound 61>

[0154]

[Chemical 56]

(1) 14.54 g (1 of a compound represented by the following formula (K2) instead of the compound represented by the above formula (A1)
00 mmol) and instead of the compound represented by the above formula (B1), 36.84 g of the compound represented by the above formula (D2)
(100 mmol) was used, and according to the method of (1) of Example 1 except that the reaction temperature was 90 ° C. instead of 80 ° C., the compound 2 of pale yellow crystal represented by the following formula (L2) was used.
0.20 g was obtained. The yield was 56.2%.

[0156]

[Chemical 57]

[0157]

[Chemical 58]

(2) In place of the compound represented by the above formula (C1), 7.19 g (20) of the compound represented by the above formula (L2)
was used according to the method of (2) of Example 1 to obtain 3.33 g of a pale yellow crystalline compound represented by the following formula (M2). The yield was 45.9%.

[0159]

[Chemical 59]

(3) In place of the compound represented by the above formula (D1), 3.76 g (10) of the compound represented by the above formula (M2)
mmol) in place of the compound represented by the above formula (E1), 2.48 g (10) of the compound represented by the above formula (N1)
(mmol) was used, and according to the method of (3) of Example 1, 2.83 g of a yellow crystal compound represented by the compound 61 was obtained. The yield was 58.4%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 485 Elemental analysis value: C ₃₅ H ₃₆ N ₂ , theoretical value (%): C = 86.73 H = 7.49 N =
5.78 Measured value (%): C = 86.75 H = 7.54 N =
5.91 (Example 11) <Synthesis of Compound 68>

[0163]

[Chemical 60]

(1) 16.56 g (1 of a compound represented by the following formula (N2) instead of the compound represented by the above formula (A1)
00 mmol) and instead of the compound represented by the above formula (B1), 36.84 g of the compound represented by the above formula (D2)
(100 mmol) was used, and represented by the following formula (O2) according to the method of (1) of Example 1 except that the reaction conditions were 100 ° C. for 4 hours instead of 80 ° C. for 5 hours. 18.59 g of a pale yellow crystalline compound was obtained. Yield 48.8
%Met.

[0165]

[Chemical formula 61]

[0166]

[Chemical formula 62]

(2) Instead of the compound represented by the above formula (C1), 7.62 g (20) of the compound represented by the above formula (O2)
was used according to the method of (2) of Example 1 to obtain 3.98 g of a pale yellow crystalline compound represented by the following formula (P2). The yield was 55.0%.

[0168]

[Chemical formula 63]

(3) 3.98 g (10) of the compound represented by the above formula (P2) instead of the compound represented by the above formula (D1)
mmol) in place of the compound represented by the above formula (E1), 2.84 g (10) of the compound represented by the following formula (Q2)
(33 mmol) was used, and according to the method of (3) of Example 1, 2.33 g of a yellow crystalline compound represented by the compound 68 was obtained. The yield was 38.0%.

[0170]

[Chemical 64]

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 613.614 Elemental analysis value: C ₄₃ H ₃₃ N ₂ Cl, theoretical value (%): C = 84.21 H = 5.43 N =
4.57 Measured value (%): C = 84.37 H = 5.43 N =
4.45 (Example 12) <Synthesis of Compound 70>

[0173]

[Chemical 65]

(1) Instead of the above formula (A1), the following formula (R
15.95 g (100 mmol) of the compound represented by 2)
Of Example 1 except that 40.44 g (100 mmol) of the compound represented by the following formula (S2) was used in place of the above formula (B1), and the reaction temperature was 100 ° C. instead of 80 ° C. According to the method of (1), 22.69 g of a pale yellow crystalline compound represented by the following formula (T2) was obtained. Yield is 5
It was 5.4%.

[0175]

[Chemical formula 66]

[0176]

[Chemical formula 67]

[0177]

[Chemical 68]

(2) Instead of the above equation (C1), the above equation (T
3.28 g of a pale yellow crystalline compound represented by the following formula (U2) according to the method of (2) of Example 1 except that 8.19 g (20 mmol) of the compound represented by 2) was used. Got The yield was 38.5%.

[0179]

[Chemical 69]

(3) Instead of the above equation (D1), the above equation (U
2.27 g (10 mmol) of the compound represented by 2) was used, and 3.21 g (10 mmol) of the compound represented by the following formula (V2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 3.01 g of a yellow crystalline compound represented by the compound 70 was obtained. Yield 44.4
%Met.

[0181]

[Chemical 70]

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 679 Elemental analysis value: C ₅₁ H ₃₈ N ₂ , theoretical value (%): C = 90.23 H = 5.64 N =
4.13 Measured value (%): C = 90.04 H = 5.52 N =
4.14 (Example 13) <Synthesis of Compound 75>

[0184]

[Chemical 71]

(1) Instead of the above formula (A1), the following formula (W
20.72 g (100 mmol) of the compound represented by 2)
Except that 29.23 g (100 mmol) of the compound represented by the following formula (X2) was used in place of the above formula (B1), and the reaction conditions were 100 ° C. for 4 hours instead of 80 ° C. for 5 hours. Was obtained according to the method of (1) of Example 1 to obtain 17.24 g of a white crystalline compound represented by the following formula (Y2). The yield was 49.9%.

[0186]

[Chemical 72]

[0187]

[Chemical formula 73]

[0188]

[Chemical 74]

(2) Instead of the above formula (C1), the above formula (Y
2.89 g of a pale yellow crystalline compound represented by the following formula (Z2) according to the method of (2) of Example 1 except that 6.90 g (20 mmol) of the compound represented by 2) was used. Got The yield was 53.6%.

[0190]

[Chemical 75]

(3) Instead of the above equation (D1), the above equation (Z
Except that 3.62 g (10 mmol) of the compound represented by 2) was used and 1.59 g (10 mmol) of the compound represented by the above formula (B2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.91 g of a yellow crystalline compound represented by the compound 75 was obtained. Yield 42.1
%Met.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 453 Elemental analysis value: C ₃₃ H ₂₈ N ₂ , theoretical value (%): C = 87.57 H = 6.24 N =
6.19 Measured value (%): C = 87.39 H = 6.15 N =
6.24 (Example 14) <Synthesis of Compound 88>

[0194]

[Chemical 76]

(1) Instead of the above formula (A1), the above formula (C
13.14 g (100 mmol) of the compound represented by 2)
Of Example 1 except that 41.85 g (100 mmol) of the compound represented by the following formula (A3) was used in place of the above formula (B1), and the reaction temperature was 100 ° C. instead of 80 ° C. According to the method of (1), 22.66 g of a pale yellow crystalline compound represented by the following formula (B3) was obtained. Yield is 5
It was 7.3%.

[0196]

[Chemical 77]

[0197]

[Chemical 78]

(2) Instead of the above formula (C1), the above formula (B
According to the method of (2) of Example 1 except that 7.91 g (20 mmol) of the compound represented by 3) was used, 4.63 g of a pale yellow crystalline compound represented by the following formula (C3). Got The yield was 56.1%.

[0199]

[Chemical 79]

(3) Instead of the above equation (D1), the above equation (C
Except that 4.13 g (10 mmol) of the compound represented by 3) was used and 2.48 g (10 mmol) of the compound represented by the above formula (N1) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.90 g of a compound of yellow crystals represented by compound 88 was obtained. Yield 36.5
%Met.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 521 Elemental analysis value: C ₃₈ H ₃₆ N ₂ , theoretical value (%): C = 87.65 H = 6.97 N =
5.38 Measured value (%): C = 87.57 H = 6.90 N =
5.50 (Example 15) <Synthesis of Compound 92>

[0203]

[Chemical 80]

(1) Instead of the above formula (A1), the above formula (C
13.14 g (100 mmol) of the compound represented by 2)
Except that 41.85 g (100 mmol) of the compound represented by the following formula (D3) was used instead of the above formula (B1), and the reaction conditions were 100 ° C. for 6 hours instead of 80 ° C. for 5 hours. Was obtained according to the method of (1) of Example 1 to obtain 18.63 g of a pale yellow crystalline compound represented by the following formula (E3). The yield was 47.1%.

[0205]

[Chemical 81]

[0206]

[Chemical formula 82]

(2) Instead of the above equation (C1), the above equation (E
3.88 g of a pale yellow crystalline compound represented by the following formula (F3) according to the method of (2) of Example 1 except that 7.91 g (20 mmol) of the compound represented by 3) was used. Got The yield was 47.1%.

[0208]

[Chemical 83]

(3) Instead of the above equation (D1), the above equation (F
Except that 3.09 g (7.5 mmol) of the compound represented by 3) was used and 2.13 g (7.5 mmol) of the compound represented by the above formula (J2) was used instead of the above formula (E1). According to the method of Example 1, (3), 1.58 g of a yellow crystalline compound represented by the compound 92 was obtained. Yield is 3
It was 3.5%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 629 Elemental analysis value: C ₄₇ H ₃₆ N ₂ , theoretical value (%): C = 89.77 H = 5.77 N =
4.45 Measured value (%): C = 89.71 H = 5.80 N =
4.53 (Example 16) <Synthesis of Compound 98>

[0212]

[Chemical 84]

(1) Instead of the above equation (A1), the above equation (K
14.54 g (100 mmol) of the compound represented by 2)
Was used, and 41.85 g (100 mmol) of the compound represented by the above formula (A3) was used in place of the above formula (B1), and the reaction temperature was 100 ° C. instead of 80 ° C. According to the method of (1), 23.88 g of a pale yellow crystalline compound represented by the following formula (G3) was obtained. Yield is 5
It was 8.3%.

[0214]

[Chemical 85]

(2) Instead of the above formula (C1), the above formula (G
4.90 g of a compound of light yellow crystals represented by the following formula (H3), according to the method of (2) of Example 1 except that 8.19 g (20 mmol) of the compound represented by 3) was used. Got The yield was 57.4%.

[0216]

[Chemical 86]

(3) Instead of the above equation (D1), the above equation (H
3.26 g (10 mmol) of the compound represented by 3) was used, and 2.48 g (10 mmol) of the compound represented by the above formula (N1) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.55 g of a yellow crystalline compound represented by the compound 98 was obtained. Yield 28.9
%Met.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 607 Elemental analysis value: C ₄₅ H ₃₈ N ₂ , theoretical value (%): C = 89.07 H = 6.31 N =
4.62 Measured value (%): C = 89.06 H = 6.33 N =
4.46 (Example 17) <Synthesis of Compound 105>

[0220]

[Chemical 87]

(1) Instead of the above formula (A1), the following formula (N
16.56 g (100 mmol) of the compound represented by 2)
Except that 41.85 g (100 mmol) of the compound represented by the above formula (A3) was used in place of the above formula (B1), and the reaction conditions were 7 hours at 120 ° C. instead of 5 hours at 80 ° C. According to the method of (1) of Example 1, 16.55 g of a pale yellow crystalline compound represented by the following formula (I3) was obtained. The yield was 38.5%.

[0222]

[Chemical 88]

(2) Instead of the above formula (C1), the above formula (I
According to the method of (2) of Example 1, except that 8.60 g (0.2 mmol) of the compound represented by 3) was used,
4.70 g of a pale yellow crystalline compound represented by the following formula (J3)
Got The yield was 52.6%.

[0224]

[Chemical 89]

(3) Instead of the above equation (D1), the above equation (J
3.47 g (10 mmol) of the compound represented by 3) was used, and 2.84 g (10 mmol) of the compound represented by the above formula (Q2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 3.51 g of a yellow crystalline compound represented by the compound 105 was obtained. The yield is 52.
It was 9%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 662.663 Elemental analysis value: C ₄₇ H ₃₅ N ₂ Cl Theoretical value (%): C = 85.15 H = 5.32 N =
4.22 Measured value (%): C = 85.21 H = 5.47 N =
4.32 (Example 18) <Synthesis of Compound 107>

[0228]

[Chemical 90]

(1) Instead of the above equation (A1), the following equation (K
15.95 g (100 mmol) of the compound represented by 3)
Except that 45.45 g (100 mmol) of the compound represented by the following formula (L3) was used in place of the above formula (B1), and the reaction conditions were 90 ° C. for 8 hours instead of 80 ° C. for 5 hours. According to the method of (1) of Example 1, 11.81 g of a yellow crystalline compound represented by the following formula (M3) was obtained. The yield was 25.7%.

[0230]

[Chemical Formula 91]

[0231]

[Chemical Formula 92]

[0232]

[Chemical formula 93]

(2) Instead of the above equation (C1), the above equation (M
According to the method of (2) of Example 1 except that 9.19 g (20 mmol) of the compound represented by 3) was used, 4.63 g of a pale yellow crystalline compound represented by the following formula (N3). Got The yield was 48.6%.

[0234]

[Chemical 94]

(3) Instead of the above equation (D1), the above equation (N
Except that 4.77 g (10 mmol) of the compound represented by 3) was used and 3.21 g (10 mmol) of the compound represented by the above formula (V2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 2.08 g of a yellow crystalline compound represented by the compound 107 was obtained. The yield is 28.
It was 6%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 729 Elemental analysis value: C ₅₅ H ₄₀ N ₂ , theoretical value (%): C = 90.63 H = 5.53 N =
3.84 Measured value (%): C = 90.67 H = 5.58 N =
3.81 (Example 19) <Synthesis of Compound 112>

[0238]

[Chemical 95]

(1) Instead of the above formula (A1), the following formula (W
20.72 g (100 mmol) of the compound represented by 2)
Was used, and 34.24 g (100 mmol) of the compound represented by the following formula (O3) was used in place of the above formula (B1), and the reaction temperature was 100 ° C. instead of 80 ° C. According to the method of (1), 10.20 g of a yellow crystalline compound represented by the following formula (P3) was obtained. The yield is 25.
It was 8%.

[0240]

[Chemical 96]

[0241]

[Chemical 97]

(2) Instead of the above formula (C1), the above formula (P
According to the method of (2) of Example 1 except that 7.91 g (20 mmol) of the compound represented by 3) was used, 4.26 g of a pale yellow crystalline compound represented by the following formula (Q3). Got The yield was 51.6%.

[0243]

[Chemical 98]

(3) Instead of the above equation (D1), the above equation (Q
Except that 4.13 g (10 mmol) of the compound represented by 3) was used and 1.59 g (10 mmol) of the compound represented by the following formula (B2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.39 g of a yellow crystalline compound represented by the compound 112 was obtained. The yield is 27.
It was 6%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 503 Elemental analysis value: C ₃₇ H ₃₀ N ₂ , theoretical value (%): C = 88.41 H = 6.02 N =
5.57 Measured value (%): C = 88.42 H = 6.05 N =
5.69 (Example 20) <Synthesis of Compound 125>

[0247]

[Chemical 99]

(1) Instead of the above formula (A1), the above formula (C
13.14 g (100 mmol) of the compound represented by 2)
Except that 29.24 g (100 mmol) of the compound represented by the following formula (R3) was used in place of the above formula (B1), and the reaction conditions were 90 ° C. for 7 hours instead of 80 ° C. for 5 hours. According to the method of (1) of Example 1, 14.51 g of a yellow crystal compound represented by the following formula (S3) was obtained. The yield was 34.6%.

[0249]

[Chemical 100]

[0250]

[Chemical 101]

(2) Instead of the above equation (C1), the above equation (S
4.47 g of a pale yellow crystalline compound represented by the following formula (T3) according to the method of (2) of Example 1 except that 8.39 g (20 mmol) of the compound represented by 3) was used. Got The yield was 51.2%.

[0252]

[Chemical 102]

(3) Instead of the above equation (D1), the above equation (T
3.37 g (10 mmol) of the compound represented by 3) was used, and 2.48 g (10 mmol) of the compound represented by the above formula (N1) was used instead of the above formula (E1).
According to the method of Example 1, (3), 2.63 g of a yellow crystal compound represented by Compound 125 was obtained. The yield is 42.
It was 6%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 617 Elemental analysis value: C ₄₆ H ₃₆ N ₂ , theoretical value (%): C = 89.58 H = 5.88 N =
4.54 Measured value (%): C = 89.69 H = 5.82 N =
4.52 (Example 21) <Synthesis of Compound 129>

[0256]

[Chemical 103]

(1) Instead of the above formula (A1), the above formula (C
13.14 g (100 mmol) of the compound represented by 2)
Was used, and 44.25 g (100 mmol) of the compound represented by the following formula (U3) was used in place of the above formula (B1), and the reaction temperature was 100 ° C. instead of 80 ° C. According to the method of (1), 22.75 g of a yellow crystalline compound represented by the following formula (V3) was obtained. The yield is 54.
It was 2%.

[0258]

[Chemical 104]

[0259]

[Chemical 105]

(2) Instead of the above formula (C1), the above formula (V
4.58 g of a pale yellow crystalline compound represented by the following formula (W3) according to the method of (2) of Example 1 except that 8.39 g (20 mmol) of the compound represented by 3) was used. Got The yield was 52.4%.

[0261]

[Chemical formula 106]

(3) Instead of the above equation (D1), the above equation (W
3.37 g (10 mmol) of the compound represented by 3) was used, and 2.84 g (10 mmol) of the compound represented by the above formula (J2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 2.29 g of a yellow crystal compound represented by the compound 129 was obtained. The yield is 35.
It was 1%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 653 Elemental analysis value: C ₄₉ H ₃₆ N ₂ , theoretical value (%): C = 90.15 H = 5.56 N =
4.29 Measured value (%): C = 90.18 H = 5.54 N =
4.21 (Example 22) <Synthesis of Compound 135>

[0265]

[Chemical formula 107]

(1) Instead of the above formula (A1), the above formula (K
14.54 g (100 mmol) of the compound represented by 2)
Except that 44.25 g (100 mmol) of a compound represented by the following formula (X3) was used in place of the above formula (B1), and the reaction conditions were 100 ° C. for 7 hours instead of 80 ° C. for 5 hours. Was obtained according to the method of (1) of Example 1 to obtain 18.90 g of a yellow crystal compound represented by the following formula (Y3). The yield was 43.6%.

[0267]

[Chemical 108]

[0268]

[Chemical 109]

(2) Instead of the above formula (C1), the above formula (Y
According to the method of (2) of Example 1, except that 8.617 g (20 mmol) of the compound represented by 3) was used,
4.61 g of a pale yellow crystalline compound represented by the following formula (Z3)
Got The yield was 51.2%.

[0270]

[Chemical 110]

(3) Instead of the above equation (D1), the above equation (Z
3) was used, except that 2.48 g (10 mmol) of the compound represented by the above formula (N1) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 2.30 g of a yellow crystalline compound represented by the compound 135 was obtained. The yield is 41.
It was 2%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 607 Elemental analysis value: C ₄₅ H ₃₈ N ₂ , theoretical value (%): C = 89.07 H = 6.31 N =
4.62 Measured value (%): C = 88.95 H = 6.35 N =
4.77 (Example 23) <Synthesis of Compound 142>

[0274]

[Chemical 111]

(1) Instead of the above formula (A1), the above formula (N
16.56 g (100 mmol) of the compound represented by 2)
Except that 44.25 g (100 mmol) of the compound represented by the above formula (X3) was used in place of the above formula (B1), and the reaction conditions were 100 ° C. for 7 hours instead of 80 ° C. for 5 hours. Was obtained according to the method of (1) of Example 1 to obtain 11.76 g of a yellow crystalline compound represented by the following formula (A4). The yield was 25.9%.

[0276]

[Chemical 112]

(2) Instead of the above formula (C1), the above formula (A
4.76 g of a pale yellow crystalline compound represented by the following formula (B4) according to the method of (2) of Example 1 except that 9.08 g (20 mmol) of the compound represented by 4) was used. Got The yield was 61.1%.

[0278]

[Chemical 113]

(3) Instead of the above equation (D1), the above equation (B
471 g (10 mmol) of the compound represented by 4) was used, and 2.84 g (10 mmol) of the compound represented by the above formula (Q2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 2.43 g of a yellow crystalline compound represented by the compound 142 was obtained. The yield is 35.
It was 3%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 686.687 Elemental analysis value: C ₄₉ H ₃₅ N ₂ Cl, theoretical value (%): C = 85.50 H = 5.12 N =
4.07 measurement value (%): C = 85.48 H = 5.26 N =
3.94 (Example 24) <Synthesis of Compound 144>

[0282]

[Chemical 114]

(1) Instead of the above formula (A1), the above formula (R
15.95 g (100 mmol) of the compound represented by 2)
Except that 47.85 g (100 mmol) of the compound represented by the following formula (C4) was used in place of the above formula (B1), and the reaction conditions were 6 hours at 100 ° C. instead of 5 hours at 80 ° C. According to the method of (1) of Example 1, 17.80 g of a yellow crystalline compound represented by the following formula (D4) was obtained. The yield was 36.8%.

[0284]

[Chemical 115]

[0285]

[Chemical formula 116]

(2) Instead of the above formula (C1), the above formula (D
According to the method of (2) of Example 1 except that 9.67 g (20 mmol) of the compound represented by 4) was used, 5.43 g of a pale yellow crystalline compound represented by the following formula (E4). Got The yield was 54.2%.

[0287]

[Chemical 117]

(3) Instead of the above equation (D1), the above equation (E
4) except that 5.01 g (10 mmol) of the compound represented by 4) was used and 3.21 g (10 mmol) of the compound represented by the above formula (U2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.93 g of a yellow crystalline compound represented by the compound 144 was obtained. The yield is 25.
It was 6%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 753 Elemental analysis value: C ₅₇ H ₄₀ N ₂ , theoretical value (%): C = 90.92 H = 5.35 N =
3.72 Measured value (%): C = 90.86 H = 5.34 N =
3.84 (Example 25) <Synthesis of compound 149>

[0291]

[Chemical 118]

(1) Instead of the above formula (A1), the above formula (W
20.72 g (100 mmol) of the compound represented by 2)
Except that 36.64 g (100 mmol) of a compound represented by the following formula (F4) was used instead of the above formula (B1), and the reaction conditions were 90 ° C. for 6 hours instead of 80 ° C. for 5 hours. According to the method of (1) of Example 1, 11.24 g of a yellow crystal compound represented by the following formula (G4) was obtained. The yield was 26.8%.

[0293]

[Chemical formula 119]

[0294]

[Chemical 120]

(2) Instead of the above formula (C1), the above formula (G
According to the method of (2) of Example 1 except that 8.39 g (20 mmol) of the compound represented by 4) was used, 4.51 g of a pale yellow crystalline compound represented by the following formula (H4). Got The yield was 51.7%.

[0296]

[Chemical 121]

(3) Instead of the above equation (D1), the above equation (H
4.37 g (10 mmol) of the compound represented by 4) was used, and 1.59 g (10 mmol) of the compound represented by the above formula (B2) was used instead of the above formula (E1).
According to the method of (3) of Example 1, 1.92 g of a yellow crystalline compound represented by the compound 149 was obtained. The yield is 36.
It was 4%.

The mass spectrum and elemental analysis values of this compound are as follows.

Mass spectrum: 527 Elemental analysis value: C ₃₉ H ₃₀ N ₂ , theoretical value (%): C = 88.94 H = 5.74 N =
5.32 Measured value (%): C = 88.89 H = 5.79 N =
5.22 (Comparative Example 1) A commercially available hydrazone compound DEH represented by the following formula (5) was used.

[0300]

[Chemical formula 122]

Comparative Example 2 A commercially available hydrazone compound SBHZ represented by the following formula (6) was used.

[0302]

[Chemical 123]

(Evaluation test) Measurement of hole mobility Using the hydrazone compounds of the present invention obtained in Examples 1 to 25 and the hydrazone compounds of Comparative Examples 1 and 2, the hole mobility was measured according to the following method. The degree was measured.

100 parts by weight of each hydrazone compound, 100 parts by weight of bisphenol A type polycarbonate, and 900 parts by weight of tetrahydrofuran were mixed,
The hydrazone compound was dissolved. This was applied onto an aluminum sheet with a bar coater # 60 and dried at 90 ° C. for 1 hour to prepare a single layer resin dispersion film with a film thickness of 8 μm. Then, a semi-transparent gold electrode was provided thereon by a vacuum vapor deposition method. Using the sandwich cell having such a structure, the hole mobility was measured as follows.

The hole mobility was measured by the conventional TOF method. The drift mobility of holes was measured by irradiating a laser beam from this electrode side with the gold electrode side as the positive electrode. At this time, the drift mobility was measured at various voltages, and a constant electric field strength (2.
Mobility (cm ² / V · se) at 5 × 10 ⁵ V / cm
c) was calculated and used as hole mobility data.

The results are shown in Table 1.

[0307]

[Table 1]

From the results shown in Table 1, the hydrazone-based compound obtained in this example maintained the same high hole mobility as that of the hydrazone-based compound of the comparative example, and showed no chemical stability. It turned out to be excellent.

(Examples 26 to 75, Comparative Examples 3 to 6) Using the hydrazone compounds of the present invention obtained in Examples 1 to 25 and the hydrazone compounds of Comparative Examples 1 and 2, the following method was followed. Single-layer type photoconductors (Examples 26 to 50, Comparative examples 3 and 4) and laminated type photoconductors (Examples 51 to 75, Comparative examples 5 and 6) were produced.

(Preparation of Single Layer Type Photoreceptor) 10 parts by weight of perylene pigment as a charge generating material and tetrahydrofuran 60
And parts by weight were dispersed for 2 hours with a paint shaker using zirconia beads (2 mm diameter). 10 parts by weight of a bisphenol A-type polycarbonate resin (Panlite L-1225, Teijin Chemicals Ltd., Panlite L-1225) in tetrahydrofuran as a binder resin, and a charge transport material 1 were added to the obtained dispersion liquid.
00 parts by weight was added, and the mixture was further dispersed for 1 hour. The obtained dispersion was applied onto an aluminum sheet using a bar coater and dried at 100 ° C. for 1 hour to form a photosensitive layer of 20 μm, and a single-layer type photoreceptor was obtained. Example 26-
As the charge transport material used in 50, the hydrazone compounds synthesized in Examples 1 to 25 were used (for example, in Example 26, the hydrazone compound synthesized in Example 1 (corresponding to compound 2) was used). The charge transporting materials used in Comparative Examples 3 and 4 were the hydrazone compounds of Comparative Examples 1 and 2 (for example, Comparative Example 3 corresponds to the hydrazone compound (DEH) of Comparative Example 1). use).

(Preparation of Laminated Photoreceptor) 100 parts by weight of dibromoanthanthrone as a charge generating material, polyvinyl butyral resin as a binder resin (“S” manufactured by Sekisui Chemical Co., Ltd.)
-LecBMS) "and 100 parts by weight of tetrahydrofuran, and zirconia beads (2 mm diameter)
It was dispersed for 2 hours with a paint shaker using. The obtained dispersion is applied onto an aluminum sheet using a bar coater and dried at 100 ° C. for 1 hour to give a film thickness of 0.5 μm.
m charge generating layer was formed.

A charge transport material 100 is formed on the charge generation layer.
A solution prepared by dissolving 100 parts by weight of bisphenol A-type polycarbonate resin (Panlite L-1225, Teijin Chemicals Co., Ltd.) in 900 parts by weight of tetrahydrofuran is applied with a bar coater and dried at 100 ° C. for 1 hour. As a result, a charge transporting layer having a film thickness of 22 μm was formed to obtain a laminated type photoreceptor. The charge transport materials used in Examples 51 to 75 are the hydrazone compounds synthesized in Examples 1 to 25 (for example, in Example 51, Example 1 is used).
The hydrazone compound (corresponding to compound 2) synthesized in 1. was used, and the charge transporting materials used in Comparative Examples 5 and 6 were the hydrazone compounds of Comparative Examples 1 and 2 (for example, in Comparative Example 5). (Corresponding to the hydrazone compound (DEH) of Comparative Example 1).

(Evaluation Test) With respect to the electrophotographic photosensitive members obtained in Examples 26 to 75 and Comparative Examples 3 to 6, the sensitivity (initial surface potential (V0), half-exposure amount (E1 / 2), and residual potential) was evaluated. (V _R)), and repetition stability was measured.

1. Measurement of Electrophotographic Characteristics 1.1 Measurement of Initial Surface Potential Each of the above electrophotographic photosensitive members was loaded in a drum sensitivity tester, and its surface was charged to a positive polarity in a single-layer type and a negative polarity in a laminated type, and then kept constant. The initial surface potential V0 (V) under corona voltage (6.5 kV) was measured.

1.2 Measurement of Half-Exposure Amount and Residual Potential Each electrophotographic photosensitive member was loaded in a drum sensitivity tester, and the electric current flowing into each electrophotographic photosensitive member was changed to charge its initial surface potential to 800V. Let Next, illuminance 10lux
1 of electrophotographic photosensitive member using white light of halogen lamp
Exposure for 0 seconds, the initial surface potential is 1/2 (400V)
The time until it becomes is defined as the half exposure time. Half-exposure amount E1 / 2 (lux · se
c) was calculated.

Furthermore, the surface potential at the time point 5 seconds after the start of exposure was measured and defined as the residual potential VR (V).

2. Measurement of Repeated Stability After the electrophotographic photoreceptors obtained in each of the above Examples and Comparative Examples were attached on an aluminum cylinder using an adhesive tape, an electrostatic copying machine DC-1670M (manufactured by Sanda Kogyo Co., Ltd.) , Modified to a variable charge polarity type),
Charging-exposure was repeated (10,000 times). Next, the electrophotographic photosensitive member was peeled off from the aluminum cylinder, and the surface potential, residual potential, and half-exposure amount before and after that were measured and calculated in the same manner as above, and the difference from the initial value was ΔV0.
(Surface potential), ΔVR (residual potential), and ΔE1 / 2 (half-exposure amount) were used to evaluate the repeated stability.

The results are shown in Table 2 (single layer type photoreceptor) and Table 3 (multilayer type photoreceptor).

[0319]

[Table 2]

[0320]

[Table 3]

From the results shown in Tables 2 and 3, the electrophotographic photosensitive member obtained in this example is of a single-layer type or a laminated type in comparison with the electrophotographic photosensitive member of the comparative example. Initial surface potential, residual potential, and half exposure E
It has been found that a value of 1/2 is also equal or superior. From the results of the repeated characteristics, it was found that the characteristics were stable without being deteriorated by the attack of ozone, nitrogen oxides, light and the like.

[0322]

INDUSTRIAL APPLICABILITY The hydrazone compound of the present invention can be used not only as a charge transport material for an electrophotographic photoreceptor, but also as a charge transport material for solar cells, EL devices and the like.

The electrophotographic photosensitive member using the hydrazone compound of the present invention uses a compound having excellent charge transporting ability and chemical stability as a charge transporting material, and thus has high sensitivity and high electrostatic charge. Excellent in characteristics and repeatability.

[Procedure amendment]

[Submission date] July 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction content]

[0001]

The present invention relates to a novel hydrazone system
The present invention relates to a compound and an electrophotographic photoreceptor using the compound .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

(Charge Transport Material) As the charge transport material, the novel hydrazone compound of the present invention is used alone or in combination of two or more. Alternatively, the novel hydrazone compounds of the present invention may be used in combination with other conventionally known charge transport materials. Conventionally known charge transport materials include, for example, 2,5-di (4-methylaminophenyl) -1,3.
Oxadiazole compounds such as 4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline Nitrogen-containing cyclic compounds such as pyrazoline compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds, etc. Compound, fused polycyclic compound
3,5,3 ', 5'-Tetraphenyl-4,4'-diff
Enoquinone, 3,5,3 ', 5'-tetramethyl-4,
4'-diphenoquinone, 3,5,3 ', 5'-tetra-t
ert-Butyl-4,4'-diphenoquinone, 3,5-
Dimethyl-3 ', 5'-ditert-butyl-4,4'
-Diphenoquinone, 3,3'-dimethyl-5,5'-di
tert-butyl-4,4'-diphenoquinone, 3,
3'-bis (α, α, γ, γ-tetramethylbutyl)-
5,5'-diphenyl-4,4'-diphenoquinone,
3,3′-bis (α, γ-dimethylbutyl) -5,5 ′
-Diphenyl-4,4'-diphenoquinone, 3,3'-
Dimethyl-5,5'-bis (α-methylbenzyl) dif
Enoquinone, 3-tert-butyl-3 ', 5,5'-
Trimethyl-4,4'-diphenoquinone, 3,5-di
Sopropyl-3'-tert-butyl-5'-phenyl
-4,4'-diphenoquinone, 3,5-diisopropyl
-3 '-(α, α, γ, γ-tetramethylbutyl)-
5'-phenyl-4,4'-diphenoquinone, 3,5-
Di (tertiary butyl) -3'-tert-butyl-5'-f
Diphenoquinones such as phenyl-4,4'-diphenoquinone
Derivatives . When a charge transporting material having film-forming property such as polyvinylcarbazole is used,
The binder resin is not always necessary.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0299

[Correction method] Change

[Correction content]

Mass spectrum: 527 Elemental analysis value: C ₃₉ H ₃₀ N ₂ , theoretical value (%): C = 88.94 H = 5.74 N =
5.32 Measured value (%): C = 88.89 H = 5.79 N =
5.22 (Comparative Example 1) Hydrazone compound represented by the following formula (5)
DEH was used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0301

[Correction method] Change

[Correction content]

(Comparative Example 2) Hydra represented by the following formula (6)
The zon compound SBHZ was used.

Claims (5)

[Claims] 1. A hydrazone compound represented by the following general formula (1): In the formula, R1 and R3 are the same or different and represent an alkyl group or an aryl group; R2 and R4 are an aryl group; R5 to R8 are the same or different and are a hydrogen atom, an alkyl group, an aryl group, Alternatively, it represents a halogen atom, and at least one of R5 to R8 is an alkyl group, an aryl group, or a halogen atom. 2. The R2 is a naphthyl group, and the R5
~ The hydrazone compound according to claim 1, wherein 3 of R8 are hydrogen atoms. 3. The hydrazone compound according to claim 1, wherein R 2 is a phenanthryl group, and three of R 5 to R 8 are hydrogen atoms. 4. The R2 is a pyrenyl group, and the R5
~ The hydrazone compound according to claim 1, wherein 3 of R8 are hydrogen atoms. 5. An electrophotographic photoreceptor having a conductive substrate and a photosensitive layer formed on the conductive substrate, the photosensitive layer comprising a charge transport material, a charge generating material, and a binder resin. And an electrophotographic photoreceptor containing the charge transporting material, which is a hydrazone compound represented by the general formula (1).