JPH06128207A - Hydrazone-based compound and electrophotographic photoreceptor using the same - Google Patents

Abstract

PURPOSE:To obtain a new hydrazone-based compound capable of providing an electrophotographic photoreceptor having high sensitivity and excellent in charging properties and repeating characteristics using as a charge-transfer material and excellent in charge-transfer ability and chemical stability. CONSTITUTION:A compound of formula I (R1 to R4 are alkyl or aryl; R5 to R8 are H, alkyl, aryl or halogen). The compound is obtained by reacting an aldehyde compound of formula II with a compound of formula III in DMF in which tert.-butoxypotassium is mixed to afford a compound of formula IV, dropping vitride into THF in which the compound is mixed, reacting the compound of formula IV with vitride and heating the resultant compound of formula V and compound of formula VI while refluxing in ethanol. A photosensitive layer containing a charge transfer material, a charge generating material and a binder resin is formed on an electrically conductive substrate to produce the objective electrophotographic photoreceptor.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel hydrazone compound and an electrophotographic photoreceptor 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, when the coating liquid for the photosensitive layer is prepared at the time of manufacturing the photoconductor, a slight amount of impurities is inevitably contained in the photoconductor manufactured at present.
Further, the photoconductor is exposed to ozone and nitrogen oxides generated by corona discharge in the charging process during the formation of a copy image, and is exposed to light in the exposure process.

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 chemical 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 to R4 are the same or different and each represents an alkyl group or an aryl group; R5 to R8
Are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.

The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a conductive substrate and a photosensitive layer formed on the conductive substrate, wherein the photosensitive layer comprises a charge transport material and a charge. The charge transport material containing a generating material and a binder resin is a compound represented by the above general formula (1), and thereby the above 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. In addition, this compound has very high stability against stress caused by light such as exposure and charge elimination. This is because the molecule has a biphenyl structure capable of obtaining a quencher effect. When such a structure is present in the molecule, the photoexcited state can be rapidly deactivated, so that it is possible to suppress the generation of a substance that becomes a deep trap that hinders electrophotographic characteristics, and it is highly suppressed against photodegradation. It is known to be effective. That is, it can be said that the hydrazone compound of the present invention has a structure having high chemical stability against light in addition to the hole transporting ability. Particularly, in the following general formula (2), which is a preferred embodiment of the present invention, R5 is 2-phenyl group (compound 38 to compound 40 described later), 3-phenyl group (compound 41 described later), and R5 is 2 -Phenyl group and R7 is 2'-
When it is a phenyl group (compound 42 described later), the chemical stability is further improved by the quencher effect.

[0017]

[Chemical 3]

In the formula, R1 to R4 are the same or different and each represents an alkyl group or an aryl group; R5 to R8
Are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.

The hydrazone compound of the present invention is excellent in compatibility with the resin because it can freely rotate at the carbon-carbon bond of the biphenyl structure.

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

[0022]

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, pyrenyl group and the like. These may have a substituent.

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

The hydrazone compound of the present invention represented by the general formula (1) is preferably represented by the general formula (2).

Specific examples of the hydrazone compound represented by the general formula (2) include R1 to R8 in the general formula (2).
Are compounds having the following substituents.

1. Compound 1 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group, R5 to R8 = hydrogen atom 1. Compound 2 R1 = methyl group, R2-R4 = phenyl group, R5-R8
= Hydrogen atom 3. Compound 3 R1 to R4 = phenyl group, R5 to R8 = hydrogen atom 4. Compound 4 R1 = methyl group, R2 = naphthyl group, R3 = methyl group,
R4 = phenyl group, R5 to R8 = hydrogen atom 5. Compound 5 R1 = methyl group, R2 = naphthyl group, R3, R4 = phenyl group, R5 to R8 = hydrogen atom 6. Compound 6 R1 = phenyl group, R2 = naphthyl group, R3, R4 = phenyl group, R5 to R8 = hydrogen atom 7. Compound 7 R1 = phenyl group, R2 = naphthyl group, R3 = phenyl group, R4 = naphthyl group, R5 to R8 = hydrogen atom Compound 8 R1 to R4 = naphthyl group, R5 to R8 = hydrogen atom 9. Compound 9 R1 = phenyl group, R2 = phenanthryl group, R3, R
4 = phenyl group, R5 to R8 = hydrogen atom 10. Compound 10 R1 = phenyl group, R2 = pyrenyl group, R3, R4 = phenyl group, R5 to R8 = hydrogen atom 11. Compound 11 R1 = ethyl group, R2 = phenyl group, R3 = ethyl group,
R4 = phenyl group, R5 to R8 = hydrogen atom 12. Compound 12 R1 = methyl group, R2 = phenyl group, R3 = ethyl group,
R4 = phenyl group, R5 to R8 = hydrogen atom 13. Compound 13 R1 to R4 = o-tolyl group, R5 to R8 = hydrogen atom 14. Compound 14 R1 to R4 = m-tolyl group, R5 to R8 = hydrogen atom 15. Compound 15 R1 to R4 = p-tolyl group, R5 to R8 = hydrogen atom 16. Compound 16 R1 = m-tolyl group, R2 = p-tolyl group, R3 = m-
16. Tolyl group, R4 = p-tolyl group, R5 to R8 = hydrogen atom 17. Compound 17 R1 to R4 = m-chloro-phenyl group, R5 to R8 = hydrogen atom 18. Compound 18 R1 to R4 = m-bromo-phenyl group, R5 to R8 = hydrogen atom 19. Compound 19 R1 to R4 = m-ethyl-phenyl group, R5 to R8 = hydrogen atom 20. Compound 20 R1 to R4 = m-trifluoromethyl-phenyl group, R
5 to R8 = hydrogen atom 21. Compound 21 R1 to R4 = m-methoxy group, R5 to R8 = hydrogen atom 22. Compound 22 R1 = trifluoromethyl group, R2 = phenyl group, R3
= Trifluoromethyl group, R4 = phenyl group, R5 to R
8 = hydrogen atom 23. Compound 23 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group, R5 = 2-methyl group, R6 = hydrogen atom, R7 = 2′-methyl group, R8 = hydrogen atom 24. Compound 24 R1 to R4 = phenyl group, R5 = 2-methyl group, R6 =
Hydrogen atom, R7 = 2′-methyl group, R8 = hydrogen atom 25. Compound 25 R1 to R4 = m-tolyl group, R5 = 2-methyl group, R6
= Hydrogen atom, R7 = 2'-methyl group, R8 = hydrogen atom 26. Compound 26 R1 = phenyl group, R2 = naphthyl group, R3, R4 = phenyl group, R5 = 2-methyl group, R6 = hydrogen atom, R7
= 2'-methyl group, R8 = hydrogen atom 27. Compound 27 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group, R5 to R8 = hydrogen atom 28. Compound 28 R1 to R4 = phenyl group, R5 to R8 = hydrogen atom 29. Compound 29 R1 to R4 = m-tolyl group, R5 to R8 = hydrogen atom 30. Compound 30 R1 = phenyl group, R2 = naphthyl group, R3, R4 = phenyl group, R5 to R8 = hydrogen atom 31. Compound 31 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = 2-chlorine atom, R6 = hydrogen atom, R7 = 2′-chlorine atom, R8 = hydrogen atom 32. Compound 32 R1 to R4 = phenyl group, R5 = 2-chlorine atom, R6 =
Hydrogen atom, R7 = 2′-chlorine atom, R8 = hydrogen atom 33. Compound 33 R1 to R4 = m-tolyl group, R5 = 2-chlorine atom, R6
= Hydrogen atom, R7 = 2'-chlorine atom, R8 = hydrogen atom 34. Compound 34 R1 = phenyl group, R2 = naphthyl group, R3, R4 = phenyl group, R5 = 2-chlorine atom, R6 = hydrogen atom, R7
= 2'-chlorine atom, R8 = hydrogen atom 35. Compound 35 R1 to R4 = phenyl group, R5 = 2-ethyl group, R6 =
Hydrogen atom, R7 = 2′-ethyl group, R8 = hydrogen atom 36. Compound 36 R1 to R4 = phenyl group, R5 = 2-methyl group, R6 =
6-methyl group, R7 = 2'-methyl group, R8 = 6'-methyl group 37. Compound 37 R1 to R4 = phenyl group, R5 = 2-bromo group, R6 =
Hydrogen atom, R7 = 2′-bromo group, R8 = hydrogen atom 38. Compound 38 R1 = methyl group, R2 = phenyl group, R3 = methyl group,
R4 = phenyl group R5 = 2-phenyl group, R6 to R8 = hydrogen atom 39. Compound 39 R1 to R4 = phenyl group, R5 = 2-phenyl group, R6
~ R8 = hydrogen atom 40. Compound 40 R1 to R4 = m-tolyl group, R5 = 2-phenyl group, R
6 to R8 = hydrogen atom 41. Compound 41 R1 to R4 = phenyl group, R5 = 3-phenyl group, R6
~ R8 = hydrogen atom 42. Compound 42 R1 to R4 = phenyl group, R5 = 2-phenyl group, R6
= Hydrogen atom, R7 = 2'-phenyl group, R8 = hydrogen atom The hydrazone compound of the present invention represented by the general formula (2) can be synthesized, for example, as follows.

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

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

In the formula, R1 and R2 are the same or different and each represents an alkyl group or an aryl group; R5 to R8
Are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom.

Next, vitrid is dropped into tetrahydrofuran in which the compound represented by the formula (c) is mixed and reacted to obtain a compound represented by the formula (d).

[0034]

[Chemical 7]

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

[0036]

[Chemical 8]

In the formula, R3 and R4 are the same or different and each represents an alkyl group or 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 in 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) As the charge generating material, selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, azo compounds, disazo compounds, phthalocyanine compounds, ansanthuron 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 the coating liquid is prepared by dissolving the charge generating material, the charge transporting material and the binder resin. 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.

[0054]

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

Example 1 <Synthesis of Compound 2>

[0056]

[Chemical 9]

(1) In 60 ml of DMF mixed with 4 g of potassium tert-butoxide, 4.02 g (20 mmol) of the compound represented by the following formula (A1) and 4.84 g (compound represented by the following formula (B1). 20 mmol) was added and the mixture was reacted at 80 ° C. for 5 hours with stirring.

[0058]

[Chemical 10]

[0059]

[Chemical 11]

Next, the obtained reaction product was poured into water, filtered, washed with water, and further washed with ethanol, and dried to give a pale yellow crystalline compound 4.0 represented by the following formula (C1).
2 g was obtained. The yield was 68.2%.

[0061]

[Chemical 12]

(2) Compound (C1) 2.9 obtained above
4 g (10 mmol) of tetrahydrofuran 100 m
It was dissolved in 1. To the obtained solution, 1.38 g (5.0 mmo of a 70% toluene solution of vitrid (sodium bis (2-methoxy) aluminum hydride) was added.
1) 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
50 ml was added dropwise, and the mixture was reacted for 15 hours with stirring. The resulting reaction product was neutralized with 40% aqueous NaOH solution,
By extracting with benzene, 1.886 g of a pale yellow crystalline compound represented by the following formula (D1) was obtained. Yield 6
It was 3.2%.

[0063]

[Chemical 13]

(3) Compound (D1) 1.1 obtained above
82 g (5 mmol) and 1.10 g (5 mmol) of the compound represented by the following formula (E1) were refluxed with 50 ml of ethanol, a small amount of acetic acid was added, and the mixture was heated under reflux for 3 hours.

[0065]

[Chemical 14]

After the reaction, water was added, the precipitate was filtered and n-
By washing with hexane, 1.08 g of a yellow crystalline compound represented by Compound 2 was obtained. Yield 54.2%
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 = 87.75 H = 5.90 N =
6.11 (Example 2) <Synthesis of Compound 6>

[0069]

[Chemical 15]

(1) 7.09 g (20) of a compound represented by the following formula (F1) instead of the compound represented by the above formula (B1)
mmol) and the reaction temperature is 100 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to 0 ° C, the compound 4.2 of pale yellow crystal represented by the following formula (G1).
6 g was obtained. The yield was 52.3%.

[0071]

[Chemical 16]

[0072]

[Chemical 17]

(2) Instead of the compound represented by the above formula (C1), 4.08 g (10) of the compound represented by the above formula (G1)
was used according to the method of (2) of Example 1 to obtain 1.94 g of a pale yellow crystalline compound represented by the following formula (H1). The yield was 47.3%.

[0074]

[Chemical 18]

(3) 1.80 g of a compound represented by the above formula (H1) in place of the compound represented by the above formula (D1) (4.
4 mmol) and 0.971 g of the compound represented by the above formula (E1) instead of 1.10 g (5 mmol).
According to the method of (3) of Example 1 except that (4.4 mmol) was used, 1.81 g of a yellow crystalline compound represented by Compound 6 was obtained. The yield was 71.2%.

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

Mass spectrum: 577 Elemental analysis value: C ₄₃ H ₃₂ N ₂ , theoretical value (%): C = 89.55 H = 5.59 N =
4.86 Measured value (%): C = 89.54 H = 5.56 N =
4.77 (Example 3) <Synthesis of Compound 13>

[0078]

[Chemical 19]

(1) Instead of the compound represented by the above formula (B1), 6.65 g (20) of the compound represented by the following formula (I1)
mmol) and the reaction temperature is 100 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to 0 ° C., the compound 4.1 of pale yellow crystal represented by the following formula (J1) was used.
3 g was obtained. The yield was 53.6%.

[0080]

[Chemical 20]

[0081]

[Chemical 21]

(2) 3.85 g (10) of the compound represented by the above formula (J1) instead of the compound represented by the above formula (C1)
2.02 g of a pale yellow crystalline compound represented by the following formula (K1) was obtained according to the method of (2) of Example 1 except that (mmol) was used. The yield was 52.1%.

[0083]

[Chemical formula 22]

(3) 1.94 g (5 m) of the compound represented by the above formula (K1) instead of the compound represented by the above formula (D1)
mol), and instead of the compound represented by the above formula (E1), 1.24 g (5 mm of the compound represented by the following formula (L1)
ol) was used, and according to the method of (3) of Example 1, compound 1.2 of a yellow crystal represented by compound 13 was used.
5 g was obtained. The yield was 42.8%.

[0085]

[Chemical formula 23]

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

Mass spectrum: 583 Elemental analysis value: C ₄₃ H ₃₈ N ₂ , theoretical value (%): C = 88.62 H = 6.57 N =
4.81 Measured value (%): C = 88.68 H = 6.63 N =
4.69 (Example 4) <Synthesis of Compound 24>

[0088]

[Chemical formula 24]

(1) 4.71 g (20) of a compound represented by the following formula (M1) instead of the compound represented by the above formula (A1)
mmol), and instead of the compound represented by the above formula (B1), 6.09 g (20) of the compound represented by the following formula (N1)
mmol) and the reaction temperature is 100 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to 0 ° C, the compound 5.1 of a pale yellow crystal represented by the following formula (O1).
9 g was obtained. The yield was 51.1%.

[0090]

[Chemical 25]

[0091]

[Chemical formula 26]

[0092]

[Chemical 27]

(2) In place of the compound represented by the above formula (C1), 3.86 g (10) of the compound represented by the above formula (O1)
2.03 g of a pale yellow crystalline compound represented by the following formula (P1) was obtained according to the method of (2) of Example 1 except that (mmol) was used. The yield was 52.2%.

[0094]

[Chemical 28]

(3) 1.94 g (5 m) of the compound represented by the above formula (P1) instead of the compound represented by the above formula (D1)
Compound (1) as a yellow crystal represented by Compound 24 according to the method of (3) of Example 1 except that the compound 1.
51 g were obtained. The yield was 54.3%.

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

Mass spectrum: 555 Elemental analysis value: C ₄₁ H ₃₄ N ₂ , theoretical value (%): C = 88.77 H = 6.18 N =
5.05 Measured value (%): C = 88.79 H = 6.28 N =
5.16 (Example 5) <Synthesis of Compound 31>

[0098]

[Chemical 29]

(1) 5.52 g (20) of a compound represented by the following formula (Q1) instead of the compound represented by the above formula (A1)
(47 mmol) was used according to the method of (1) of Example 1 to obtain 3.47 g of a pale yellow crystalline compound represented by the following formula (R1). The yield was 47.6%.

[0100]

[Chemical 30]

[0101]

[Chemical 31]

(2) 3.00 g of the compound represented by the above formula (R1) instead of the compound represented by the above formula (C1) (8.
According to the method of (2) of Example 1 except that 24 mmol) was used, 2.13 g of a pale yellow crystalline compound represented by the following formula (S1) was obtained. The yield was 70.4%.

[0103]

[Chemical 32]

(3) Instead of the compound represented by the above formula (D1), 1.83 g (5 m of the compound represented by the above formula (S1)
mol), and 0.793 g (5 m of the compound represented by the following formula (T1) instead of the compound represented by the above formula (E1).
Compound (1) of yellow crystals represented by Compound 31 according to the method of (3) of Example 1 except that the compound 1.
11 g were obtained. The yield was 47.2%.

[0105]

[Chemical 33]

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

Mass spectrum: 471.472 Elemental analysis value: C ₂₉ H ₂₄ N ₂ Cl ₂ , theoretical value (%): C = 73.92 H = 5.13 N =
5.94 Measured value (%): C = 73.87 H = 5.04 N =
5.86 (Example 6) <Synthesis of Compound 36>

[0108]

[Chemical 34]

(1) 7.75 g (20) of a compound represented by the following formula (U1) in place of the compound represented by the above formula (A1)
mmol), and instead of the compound represented by the above formula (B1), 6.09 g (20) of the compound represented by the above formula (N1)
mmol) and the reaction temperature was 120 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to 0 ° C, the compound 4.3 of the pale yellow crystal represented by the following formula (V1).
7 g was obtained. The yield was 40.6%.

[0110]

[Chemical 35]

[0111]

[Chemical 36]

(2) In place of the compound represented by the above formula (C1), 4.00 g of the compound represented by the above formula (V1) (7.
(2 mmol) of Example 1 except that 44 mmol) was used.
According to the above method, 1.55 g of a pale yellow crystalline compound represented by the following formula (W1) was obtained. The yield was 39.8%.

[0113]

[Chemical 37]

(3) 1.50 g of a compound represented by the above formula (W1) in place of the compound represented by the above formula (D1) (2.
87 mmol) and 0.631 g of the compound represented by the above formula (E1) instead of 1.10 g (5 mmol).
According to the method of (3) of Example 1 except that (2.87 mmol) was used, 1.04 g of a yellow crystalline compound represented by the compound 36 was obtained. The yield was 51.4%.

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

Mass spectrum: 707 Elemental analysis value: C ₅₃ H ₄₂ N ₂ , theoretical value (%): C = 90.05 H = 5.99 N =
3.96 Measured value (%): C = 89.93 H = 5.93 N =
3.90 (Example 7) <Synthesis of Compound 40>

[0117]

[Chemical 38]

(1) 5.66 g (20) of a compound represented by the following formula (X1) instead of the compound represented by the above formula (A1)
mmol), and instead of the compound represented by the above formula (B1), 6.65 g (20) of the compound represented by the above formula (I1).
mmol) and the reaction temperature is 100 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to ° C, the compound 5.8 of a pale yellow crystal represented by the following formula (Y1).
4 g was obtained. The yield was 63.3%.

[0119]

[Chemical Formula 39]

[0120]

[Chemical 40]

(2) 4.62 g (10) of a compound represented by the following formula (Y1) instead of the compound represented by the above formula (C1)
(44 mmol) was used, and according to the method of (2) of Example 1, 2.44 g of a pale yellow crystalline compound represented by the following formula (Z1) was obtained. The yield was 52.7%.

[0122]

[Chemical 41]

(3) In place of the compound represented by the above formula (D1), 2.32 g (5 m) of the compound represented by the above formula (Z1)
mol), and instead of the compound represented by the above formula (E1), 1.24 g (5 mm of the compound represented by the above formula (L1).
ol) was used, and according to the method of (3) of Example 1, compound 1.1 of a yellow crystal represented by compound 40 was used.
9 g was obtained. The yield was 36.1%.

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 = 89.22 H = 6.46 N =
4.21 (Example 8) <Synthesis of Compound 41>

[0126]

[Chemical 42]

(1) Instead of the compound represented by the above formula (A1), 5.66 g (20) of the compound represented by the following formula (A2)
mmol), and instead of the compound represented by the above formula (B1), 6.09 g (20) of the compound represented by the above formula (N1)
mmol) and the reaction temperature is 100 ° C instead of 80 ° C.
According to the method of (1) of Example 1 except that the temperature was set to 0 ° C, the compound 4.1 of pale yellow crystal represented by the following formula (B2).
1 g was obtained. The yield was 47.5%.

[0128]

[Chemical 43]

[0129]

[Chemical 44]

(2) Instead of the compound represented by the above formula (C1), 4.00 g of the compound represented by the above formula (B2) (9.
22 mmol) was used, but (2) of Example 1 was used.
According to the method of 2., 2.21 g of the compound of pale yellow crystal represented by the following formula (C2) was obtained. The yield was 54.8%.

[0131]

[Chemical formula 45]

(3) Instead of the compound represented by the above formula (D1), the compound represented by the above formula (C2) 2.18 g (5 m
Compound (1) of yellow crystals represented by Compound 41, according to the method of (3) of Example 1 except that the compound 1.
10 g were obtained. The yield was 36.6%.

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

Mass spectrum: 603 Elemental analysis value: C ₄₅ H ₃₄ N ₂ , theoretical value (%): C = 89.67 H = 5.69 N =
4.65 Measured value (%): C = 89.62 H = 5.79 N =
4.51 (Example 9) <Synthesis of Compound 42>

[0135]

[Chemical formula 46]

(1) 7.19 g (20) of a compound represented by the following formula (D2) instead of the compound represented by the above formula (A1)
mmol), and instead of the compound represented by the above formula (B1), 6.09 g (20) of the compound represented by the above formula (N1)
mmol) and the reaction conditions were 120 ° C. for 7 hours instead of 80 ° C. for 5 hours, according to the method of (1) of Example 1 and represented by the following formula (E2). 5.82 g of yellow crystalline compound was obtained. The yield was 57.1%.

[0137]

[Chemical 47]

[0138]

[Chemical 48]

(2) Instead of the compound represented by the above formula (C1), 5.09 g (10) of the compound represented by the above formula (E2)
2.37 g of a pale yellow crystalline compound represented by the following formula (F2) was obtained according to the method of (2) of Example 1 except that (mmol) was used. The yield was 46.2%.

[0140]

[Chemical 49]

(3) In place of the compound represented by the above formula (D1), 2.20 g of the compound represented by the above formula (F2) (4.
3 mmol) and 0.949 g of the compound represented by the above formula (E1) instead of 1.10 g (5 mmol).
According to the method of (3) of Example 1 except that (4.3 mmol) was used, 1.25 g of a yellow crystalline compound represented by the compound 42 was obtained. The yield was 42.9%.

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 = 90.28 H = 5.65 N =
4.29 (Comparative Example 1) A commercially available hydrazone compound DEH represented by the following formula (3) was used.

[0144]

[Chemical 50]

Comparative Example 2 A commercial hydrazone compound SBHZ represented by the following formula (4) was used.

[0146]

[Chemical 51]

(Evaluation test) Measurement of hole mobility Using the hydrazone compounds of the present invention obtained in the above Examples 1 to 9 and the hydrazone compounds of Comparative Examples 1 and 2, the hole transfer was conducted according to the following method. The degree was measured.

100 parts by weight of each of the above hydrazone compounds, 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.

[0151]

[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 10 to 27, Comparative Examples 3 to 6) Using the hydrazone compounds of the present invention obtained in Examples 1 to 9 and the hydrazone compounds of Comparative Examples 1 and 2, the following method was followed. Single-layer type photoconductors (Examples 10 to 18, Comparative examples 3 and 4) and laminated type photoconductors (Examples 19 to 27, Comparative examples 5 and 6) were produced.

(Production 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 10
As the charge transport material used in 18, the hydrazone compounds synthesized in Examples 1 to 9 are used (for example,
In Example 10, the hydrazone compound (corresponding to compound 2) synthesized in Example 1 was used), and as the charge-transporting material used in Comparative Examples 3 and 4, the hydrazone compound of Comparative Examples 1 and 2 was used (respectively). For example, in Comparative Example 3, the hydrazone compound (DEH) of Comparative Example 1 is used). (Production of Laminated Photoreceptor) 100 parts by weight of dibromoanthanthurone as a charge generating material, polyvinyl butyral resin as a binder resin (“S-lecBM” manufactured by Sekisui Chemical Co., Ltd.)
S) ”100 parts by weight, and tetrahydrofuran 120
Part by weight was dispersed for 2 hours on a paint shaker using zirconia beads (2 mm diameter). The obtained dispersion is coated on an aluminum sheet using a bar coater,
After drying at 100 ° C. for 1 hour, a charge generation layer having a film thickness of 0.5 μm was formed.

The 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. As the charge transporting materials used in Examples 19 to 27, the hydrazone compounds synthesized in Examples 1 to 9 were used (for example, in Example 19, the hydrazone compound synthesized in Example 1 (corresponding to Compound 2 was used. ) Is used), and the hydrazone compounds of Comparative Examples 1 and 2 are used as the charge transporting materials used in Comparative Examples 5 and 6 (for example, in Comparative Example 5, the hydrazone compound (DEH) of Comparative Example 1 is used. Equivalent))).

(Evaluation Test) With respect to the electrophotographic photosensitive members obtained in Examples 10 to 27 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 cyclic stability were measured respectively.

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, the current flowing into each electrophotographic photosensitive member was changed, and its initial surface potential was charged 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.

Further, the surface potential at the time point 5 seconds after the start of exposure was measured, and the result was taken 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).

[0162]

[Table 2]

[0163]

[Table 3]

From the results shown in Tables 2 and 3, the electrophotographic photoreceptors obtained in this example are of a single-layer type or a laminated type in comparison with the electrophotographic photoreceptors of Comparative Examples. 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.

[0165]

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

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 therefore 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] 0048

[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 Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0143

[Correction method] Change

[Correction content]

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 = 90.28 H = 5.65 N =
4.29 (Comparative Example 1) Hydrazone compound represented by the following formula (3)
DEH was used.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0145

[Correction method] Change

[Correction content]

(Comparative Example 2) Hydra represented by the following formula (4)
The zon compound SBHZ was used.

Claims (2)

[Claims] 1. A hydrazone compound represented by the following general formula (1): In the formula, R1 to R4 are the same or different and represent an alkyl group or an aryl group; R5 to R8 are the same or different and represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom. 2. An electrophotographic photoreceptor having a conductive substrate and a photosensitive layer formed on the conductive substrate, wherein the photosensitive layer is 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).