JPH07291876A - Cyclopentadiene compound and electrophotographic photoreceptor containing the same - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] To provide a novel compound used as an acceptor compound in an electrophotographic photoreceptor. [Structure] General formula (I) Specifically, for example A cyclopentadiene compound represented by: and an electrophotographic photoreceptor containing the same in a photosensitive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclopentadiene compound, and the compound of the present invention is used as a novel electron transporting acceptor compound in electrophotographic photoreceptors such as copying machines and printers.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive layer of an electrophotographic photoreceptor,
Inorganic photoconductive substances such as selenium, selenium-tellurium alloy, and zinc oxide have been widely used, but in recent years, research on electrophotographic photoreceptors using organic photoconductive substances has progressed, and some of them have been put to practical use. ing. Most of the photoconductors that have been put into practical use here are laminated electrophotographic photoconductors that are composed of a photosensitive layer having a charge generation layer and a charge transport layer, and a photoconductor that is made of an inorganic photoconductive substance. The sensitivity and life of the photoconductor, which were inferior to those in comparison, were improved, and electrophotographic photoconductors were actively designed at low cost, taking advantage of the advantages of organic photoconductive materials such as safety and versatility. It was This type of multi-layer electrophotographic photoreceptor is generally one in which a charge generating layer made of a charge generating substance such as a pigment and a dye, and a charge transporting layer made of a charge transporting substance such as hydrazone and pyrazoline are sequentially formed on a conductive support. Due to the nature of the electron transporting charge transport material, it is of the hole transfer type and has sensitivity when negatively charged on the surface of the photoreceptor. However, with negative charging, the corona discharge used during charging is more unstable than with positive charging,
There is a problem in that ozone, nitrogen oxides, etc., which are about 10 times as much as in the case of positive charging, are generated and adsorbed on the surface of the photoconductor to easily cause physical deterioration or chemical deterioration and further deteriorate the environment. Another problem is that the development of the negative charging photoreceptor requires a positive polarity toner, but the positive polarity toner is difficult to manufacture in view of the triboelectrification series with respect to the ferromagnetic carrier particles, and has a high two-component high resistance. In the magnetic brush developing method, the negatively charged toner / developer is more stable, and the degree of freedom in selection and use conditions is larger, and in this respect, the application range is wide and advantageous for the positively charged type photoreceptor.

Therefore, it has been proposed to use a photoconductor using an organic photoconductive material with positive charging. For example, when a photoconductor is formed by laminating a charge transport layer on the charge generation layer, the charge transport layer has a large electron transport ability, for example, 2, 4, 7
-Trinitro-9-fluorenone and the like are used, but it has been pointed out that the substance has carcinogenicity, and there is a problem that it is extremely unsuitable for occupational health. Further, as an electron transport compound, a fluorenylidene methane compound is disclosed in JP-A-60-69657, and a JP-A-61-23375.
No. 0, anthraquinodimethane and anron derivatives are used, but both of them have a problem in their repeating characteristics. JP-A-5-25136 discloses a naphthalenedicarboxylic acid imide compound, and JP-A-5-25174 discloses a naphthalenetetraimide. Although a carboxylic acid diimide compound is used,
Both of these have problems such as insufficient sensitivity and poor compatibility with the binder resin. Further, U.S. Pat. No. 3,615,414 discloses a positively charged photoreceptor containing thiapyrylium salt (charge generating substance) so as to form a eutectic complex with polycarbonate (binder resin). However, this known photoconductor has a drawback that a memory phenomenon is large and a ghost is easily generated.

Therefore, a charge generating layer containing a charge generating substance that generates holes and electrons upon irradiation with light is an upper layer (surface layer), and a charge transporting layer containing a charge transporting substance having a hole transporting ability is a lower layer. It is considered that a photoreceptor having a laminated photosensitive layer can be used for positive charging. However, since the layer for containing the charge generating substance is formed as the surface layer in the positive charging photoreceptor, single wavelength light irradiation such as ultraviolet light irradiation during light irradiation,
A charge generating substance vulnerable to external action such as corona discharge, humidity and mechanical friction will be present in the vicinity of the surface layer, and electrophotographic performance will be deteriorated during storage of the photoconductor and during image formation, resulting in poor image quality. Will start to decline. In the conventional negative charging photoreceptor having the charge transport layer as the surface layer, the influence of the various external effects is extremely small, and rather the charge transport layer has a function of protecting the lower charge generating layer.

Therefore, for example, it is possible to provide a thin protective layer made of an insulative and transparent resin to protect the layer containing the charge generating substance from an external action. However, the charge generated during light irradiation is blocked by the protective layer. As a result, the light irradiation effect is lost, and if the thickness of the protective layer serving as the surface layer is large, the sensitivity is lowered. As described above, various attempts have been made to obtain a photoconductor for positive charging, but all of them have many problems to be solved in terms of photosensitivity, memory phenomenon, industrial hygiene and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly sensitive and durable electrophotographic photoreceptor, which comprises a conductive support and a photosensitive layer formed thereon as an essential component. is there. Particularly, it is to provide a high-performance charge-transporting acceptor compound having good compatibility with a binder resin.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention in synthesizing a specific group of compounds. That is, the first invention of the present application is a cyclopentadiene compound represented by the general formula (I).

[0008]

[Chemical 3]

The second invention of the present application is such that a conductive support and a photosensitive layer formed thereon are essential components, and the cyclopentadiene compound represented by the general formula (I) is contained in the photosensitive layer. It is an electrophotographic photosensitive member containing. Here, in the formula, R ₁ and R ₄ are the same or different and each is a hydrogen atom-substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group,
A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted acyl group, a cyano group,
It represents at least one group selected from the group consisting of a nitro group and a halogen atom. R ₂ and R ₃ are the same or different and each is at least one group selected from the group consisting of a hydrogen atom-substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, and a substituted or unsubstituted heterocyclic group. Represent.

X represents ═O and at least one group selected from the group consisting of groups represented by the following formulas (II) and (III). = C (A) (B) (II) = N-R 5 (III) [wherein in (II) A, B are the same or different hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted aromatic group, and represents at least one group selected from the group consisting of -COOR _6. R ₅ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a cyano group. R ₆ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group. These substituents will be described with examples.

In R ₁ and R ₄ in the above formula (I), the substituted or unsubstituted alkyl group is a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, a hexyl group or an octyl group. And the like, a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, a halogen-substituted alkyl group such as a trifluoromethyl group, a chloromethyl group, a bromoethyl group and a fluoropropyl group, and a benzyl group. Examples of the substituted or unsubstituted aromatic group include aromatic groups such as phenyl group, naphthyl group, anthracene group and pyrene group, and the substituents thereof include chloro group, bromo group, methyl group, ethyl group and isopropyl group. Group, t-butyl group, n-butyl group, nitro group, cyano group, methoxy group, ethoxy group, acetoxy group, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, methylcarbonyl group, ethylcarbonyl group, N, N -Dimethylamino group,
Benzooxyamino group, N, N-dimethylamide group, methylthioxy group, trifluoromethyl group, phenyl group,
Etc. are illustrated respectively.

As the substituted or unsubstituted heterocyclic group,
Examples thereof include a furan group, a thiophene group, a pyridine group, a benzofuran group, a benzothiophene group, a quinoxaline group, and a piperan group, and the substituents thereof include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an n-butyl group. ,
Examples thereof include a chloro group, a bromo group, a nitro group, a cyano group and a methoxycarbonyl group. Examples of the substituted or unsubstituted alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group, a 3-chlorobutoxycarbonyl group, and a 4-methylphenoxycarbonyl group.
Each is illustrated. The substituted or unsubstituted carbamoyl group means N, N-dimethylcarbamoyl group, N, N-
Examples thereof include dihexylcarbamoyl group, N-ethylcarbamoyl group, and N, N-ditolylcarbamoyl group.

Examples of the substituted or unsubstituted acyl group include a methylcarbonyl group, an ethylcarbonyl group, a hexylcarbonyl group and a tolylcarbonyl group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. In R ₂ and R ₃ in the above formula (I), a substituted or unsubstituted alkyl group, aromatic group,
Examples of the heterocyclic group are the same as those of R ₁ and R ₄ mentioned above. Examples of the substituted or unsubstituted aromatic group in A and B in the above formula (II) are the same as those of R ₁ and R ₄ mentioned above. In R ₅ and R ₆ in the above formulas (II) and (III), examples of the substituted or unsubstituted alkyl group and aromatic group are the same as those of R ₁ and R ₄ described above. Specific examples of the cyclopentadiene compound of the general formula (I) of the present invention are shown in Table 1, but not limited thereto.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7]

[0021]

[Table 8]

[0022]

[Table 9]

[0023]

[Table 10]

[0024]

[Table 11]

[0025]

[Table 12]

The compound of the general formula (I) can be produced by any known method, for example, by reacting a corresponding ketone compound and a dione compound in the presence of a basic catalyst according to the following reaction formula. It can be obtained from the obtained pentadienone compound (I ′).

[0027]

[Chemical 4]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above) The basic catalyst used in the above reaction includes N-methylmorpholine, N-methylpiperidine, pyridine and piperidine. , Or an organic base such as triethylamine,
Examples thereof include acetates such as sodium acetate, potassium acetate or ammonium acetate, and inorganic bases such as sodium carbonate or potassium carbonate. The reaction is usually solvent-free, or methanol, ethanol, isopropanol, butanol, acetic acid, tetrahydrofuran, 1,4-
It can be carried out in a polar solvent such as dioxane or N, N-dimethylformamide, or an aromatic solvent such as benzene, toluene, chlorobenzene or xylene.
The reaction temperature is room temperature to 150 ° C, preferably room temperature to 100 ° C
Done in. The pentadienone compound of the general formula (I ′) synthesized as described above is used as malononitrile represented by the following formula (1), alkylcyanoacetic acid represented by the following formula (2), and allylacetonitrile represented by the following formula (3). , A dialkyl malonate represented by the following formula (4)

[0029]

[Chemical 5]

(Wherein R ₆ is as defined above, R is as defined for R ₁ ) and the like, in the presence of an acidic catalyst or a basic catalyst,
By reacting, the pentadiene compound of the present invention can be obtained. Examples of the acidic catalyst used in the reaction include Lewis acids such as titanium tetrachloride, zinc chloride, aluminum chloride and boron trifluoride, and examples of the basic catalyst include N-methylmorpholine, N-methylpiperidine, Examples thereof include organic bases such as pyridine, piperidine and triethylamine, acetates such as sodium acetate, potassium acetate and ammonium acetate, and inorganic bases such as sodium carbonate and potassium carbonate. The reaction is usually solvent-free, or a halogen-based solvent such as dichloromethane or dichloroethane, tetrahydrofuran,
It can be carried out in an ether solvent such as dioxane or an aromatic solvent such as benzene and toluene. The reaction temperature is -20 ° C to 150 ° C, preferably 0 ° C to 10 ° C.
It is carried out at 0 ° C. Further, the cyclopentadienone compound represented by the general formula (I ′) is an aniline compound represented by the following formula (5): H ₂ N—R ₅ (5) (wherein R ₅ has the same meaning as described above, provided that R ₅ When is a cyano group, the method shown below is preferable.) In the presence of an acidic catalyst to obtain the pentadiene compound of the present invention. Examples of the acidic catalyst used in the reaction include Lewis acids such as titanium tetrachloride, zinc chloride, aluminum chloride and boron trifluoride.

The reaction can be carried out usually without solvent, in a halogen solvent such as dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or dioxane, or an aromatic solvent such as benzene or toluene. Reaction temperature is -20 ° C to 150 ° C, preferably 0 ° C
To 100 ° C. Further, the cyclopentadienone compound represented by the general formula (I ′) is replaced by a diimide compound (CH ₃ ) ₃ Si—N═C═N—Si (CH ₃ ) ₃ (6) represented by the following formula (6) and an acidic catalyst. The pentadiene compound of the present invention can be obtained by reacting in the presence of. Examples of the acidic catalyst used in the reaction include Lewis acids such as titanium tetrachloride, zinc chloride, aluminum chloride and boron trifluoride. The reaction can usually be carried out without a solvent, in a halogen solvent such as diloromethane or dichloroethane, an ether solvent such as tetrahydrofuran or dioxane, or an aromatic solvent such as benzene or toluene. The reaction temperature is 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C. Further, the cyclopentadiene compound of the present invention can be used not only as a charge-transporting substance for an electrophotographic photoreceptor, but also as an electronic device such as a solar cell and an organic EL device in the electronics field. Next, the structure of the electrophotographic photosensitive member of the present invention will be described with reference to the drawings.

As the electrophotographic photosensitive member, for example, as shown in FIG. 1, a support 1 (a conductive support or a sheet on which a conductive layer is provided) contains a charge generating substance and optionally a binder resin. A layer (charge generating layer) 2 is provided as a lower layer, and a photosensitive layer 4 having a layered structure is provided in which a layer (charge transporting layer) 3 containing a charge transporting material and optionally a binder resin is provided as an upper layer, as shown in FIG. The protective layer 5 on the photosensitive layer 4 of FIG.
And a photosensitive layer 6 having a single-layer structure containing a charge generating substance, a charge transporting substance and, if necessary, a binder resin on a support as shown in FIG. 3, a protective layer may be provided on the upper layer of the single-layered photoreceptor 6 and an intermediate layer may be provided between the support and the photosensitive layer. As the charge generating substance used in the electrophotographic photosensitive member of the present invention, both an inorganic substance and an organic substance can be used as long as they absorb visible light and generate a free charge. For example, amorphous selenium, trigonal selenium, selenium-arsenic alloy, selenium-tellurium alloy,
Inorganic substances such as cadmium sulfide, cadmium selenide, cadmium sulphide selenide, mercury sulfide, lead oxide, lead sulfide, and amorphous silicon, or bisazo dyes, polyazo dyes, triarylmethane dyes, thiazine dyes, oxazine dyes , Xanthene dyes, cyanine dyes,
Styryl dyes, pyrylium dyes, quinacridone dyes, indigo dyes, perylene dyes, polycyclic quinone dyes, bisbenzimidazole dyes, indanthrone dyes, squarylium dyes, anthraquinone dyes,
And organic substances such as phthalocyanine dyes.

The binder resin usable in the photosensitive layer of the electrophotographic photoreceptor of the present invention includes, for example, polyethylene, polypropylene, acrylic resin, methacrylic resin,
Vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin,
Addition polymerization type resins such as melamine resins, polyaddition type resins, polycondensation type resins, and copolymer resins containing two or more repeating units of these resins, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride In addition to an insulating resin such as a vinyl acetate-maleic anhydride copolymer resin, a polymer organic semiconductor such as poly-N-vinylcarbazole may be used. The conductive support for supporting the photosensitive layer, aluminum, a metal plate such as nickel, a metal drum or a metal foil,
Plastic film deposited with aluminum, tin oxide, indium oxide, etc. or paper coated with a conductive material,
Films such as plastic or drums can be used. Next, the production of the electrophotographic photosensitive member of the present invention will be described.

When the electrophotographic photosensitive member according to the present invention has a laminated structure of a charge generation layer and a charge transport layer, that is, the structure shown in FIGS. 1 and 2, first, the charge generation layer is formed on the conductive support. Form. The charge-generating layer is formed by vacuum-depositing a charge-generating substance on a conductive support, or by coating or drying a solution prepared by dissolving or dispersing it in a suitable solvent alone or together with a suitable binder resin, and drying it. It can be formed similarly to the transport material. When the charge generating layer is formed by dispersing the charge generating substance, it is preferable that the charge generating substance is a granular material having an average particle diameter of 2 μm or less, preferably 1 μm or less. That is, if the particle size is too large, the dispersion in the layer becomes poor, and the particles partially project on the surface and the surface smoothness deteriorates. Toner filming phenomenon tends to occur due to particles adhering. However, if the above-mentioned particle size is too small, it tends to agglomerate rather, the resistance of the layer increases, the crystal defects increase and the sensitivity and repeatability deteriorate, or there is a limit in miniaturization. The lower limit of the diameter is preferably 0.01 μm. The charge generation layer can be provided by the following method. That is, this is a method in which the charge generating substance is made into fine particles in a dispersion medium by a ball mill, a homomixer, etc., and a dispersion liquid obtained by mixing and dispersing a binder resin and applying the dispersion liquid is applied. In this method, if the particles are dispersed under the action of ultrasonic waves, uniform dispersion is possible. In the charge generation layer, the ratio of the charge generation substance contained in the binder resin is
The amount is 20 to 200 parts by weight with respect to 100 parts by weight of the binder resin.

The thickness of the charge generation layer formed as described above is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm. The charge-transporting layer is provided by a method in which the charge-transporting material of the present invention is dissolved or dispersed in a suitable solvent alone or together with a suitable binder resin, and the resulting solution is applied onto the charge-generating layer and dried. Examples of the solvent used for the charge transport layer include N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, dichloromethane, 1,
Examples thereof include 1,1-trichloroethane, 1,1,2-trichloroethylene, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ethyl acetate and butyl acetate. In the charge transport layer, the ratio of the charge transport substance contained in the binder resin is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the binder resin.

The thickness of the charge transport layer is preferably 5 to 50.
μm, particularly preferably 5 to 30 μm. Next, in the case where the electrophotographic photosensitive member according to the present invention has a single layer structure, that is, the structure shown in FIG. 3, the charge generating substance and the charge transporting substance according to the present invention are dissolved or dispersed together with a binder resin to make the conductive material. It can be formed by a method of coating on a support and drying. The ratio of the charge generation material and the charge transport material contained in the binder resin is 100% by weight.
It is preferable that the charge generating substance is 20 to 200 parts by weight and the charge transporting substance is 20 to 200 parts by weight with respect to parts by weight.
The film thickness of the single-layer photosensitive member is 7 to 50 μm, more preferably 10 to 30 μm.

Further, the intermediate layer functions as an adhesive layer or a barrier layer, and in addition to the above binder resin, for example, polyvinyl alcohol, ethyl cellulose,
Resins such as carboxymethyl cellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, N-alkoxymethyl nylon as they are, or those in which tin oxide or indium is dispersed, A deposited film of aluminum oxide, zinc oxide, silicon oxide, or the like is used. The thickness of the intermediate layer is preferably 1 μm or less. As the material used for the protective layer, it is suitable to use the above-mentioned resin as it is or to disperse a low resistance substance such as tin oxide or indium oxide. Further, an organic plasma-polymerized film can also be used, and the organic plasma-polymerized film may optionally contain oxygen, nitrogen, halogen, and Group III and Group V atoms of the periodic table.

[0038]

EXAMPLES The present invention will be described below based on examples.
The invention is not limited to these examples. The examples of the cyclopentadiene compound of the present invention are referred to as "synthesis examples" and are distinguished from the "examples" of the electrophotographic photoreceptor. "Parts" in the examples are "parts by weight" unless otherwise specified. Synthesis Example 1 [Synthesis of Compound of Structural Formula (42)] 3.3 g (0.01 mol) of commercially available dimethyl-4,4′-benzyldicarboxylate and 2.1 g (0.01 mol) of dibenzyl ketone were added to ethanol. Dissolve it in 150 ml, and add 3.2 g (0.02 mo
l) was added, and the mixture was stirred and refluxed for 2 hours. After the reaction, the mixture was allowed to cool to room temperature, transferred to an aqueous layer, and extracted with chloroform. After the chloroform layer was dried over anhydrous magnesium sulfate, chloroform was distilled off, and then the residue was subjected to silica gel chromatography using 1,2-dichloroethane as a developing solvent, and the obtained crude target product was regenerated from ethanol. Crystallized pure target 1.0g
Got Melting point 176.0-177.1 [deg.] C. The elemental analysis values of C are 79.35 (79.19) and H are 5.12 (4.8).
It became 3), and they agreed. [The values in () are theoretical values. 〕Also,
The infrared spectrum diagram of this product is shown in FIG.

Synthesis Example 2 [Synthesis of Compound of Structural Formula (43)] 2.5 g of the compound of structural formula (42) obtained in Synthesis Example 1
(0.005 mol) and commercially available butyl cyanoacetate 1.
4 g (0.01 mol) was dissolved in dichloromethane, 1.9 g (0.01 mol) of titanium tetrachloride was added dropwise under stirring with ice cooling, and then 4.1 g (0.0 mol) of N-methylmorpholine.
(4 mol) was added dropwise, and the mixture was further stirred at room temperature for 5 hours.
This was transferred to an aqueous layer and extracted with chloroform. After the chloroform layer was dried over anhydrous magnesium sulfate, chloroform was distilled off, and then the residue was subjected to silica gel column chromatography using 1,2-dichloroethane as a developing solvent to obtain the crude target product from ethanol. Recrystallization gave 2.4 g of the pure target product. Melting point 15
7.5 to 159.0 ° C., elemental analysis C is 76.89
(77.03), H is 5.28 (5.33), and N is 2.
It was 32 (2.25), which was in agreement [inside of () is theoretical value. ]. The infrared absorption spectrum of this product is shown in FIG.

Example 1 5 parts of bisazo dye represented by the following chemical formula (IV), 2.5 parts of butyral resin (Denka butyral resin # 3000-2: manufactured by Denki Kagaku Kogyo), and 9 parts of tetrahydrofuran
2.5 parts were dispersed in a ball mill for 12 hours, and then tetrahydrofuran was added so that the concentration of the dispersion liquid was 2% by weight and redispersed to prepare a coating liquid. The prepared dispersion liquid was cast and coated on a 100 μm-thick polyester film on which aluminum was vapor-deposited by a doctor blade to form a charge generation layer having a film thickness after drying of 1.0 μm.

[0041]

[Chemical 6]

On the charge generation layer thus obtained,
6 parts of an exemplified compound (compound No. 1), 10 parts of a polycarbonate resin [K-1300: manufactured by Teijin Chemicals Ltd.], 0.002 parts of methylphenylsilicone [KF50-100 cps: manufactured by Shin-Etsu Chemical Co., Ltd.], and A coating solution having a formulation of 94 parts of tetrahydrofuran was prepared and cast-coated with a docker blade to form a charge transport layer having a film thickness after drying of 20.0 μm. Aluminum electrode / charge generation layer / charge transport layer A laminated electrophotographic photoconductor (photoconductor N
o.1) was created.

Examples 2 to 7 Instead of the exemplified compound (Compound No. 1) of Example 1, compound No. 2, compound No. 19 and compound N in the exemplified compound were used.
o.26, compound No. 27, compound No. 42, compound No.
Photosensitive member No. 2, photosensitive member No. 3, photosensitive member No. 4, photosensitive member No. 5, in the same manner as in Example 1 except that 43 is used.
Photosensitive member No. 6 and photosensitive member No. 7 were prepared. Comparative Example 1 Example 1 was repeated except that 2,4,7-trinitrofluorenone (TNF) was used in place of the exemplified compound of Example 1.
Photosensitive member No. 8 was prepared by the same method as described above.

Example 8 A charge generation layer was prepared in the same manner as in Example 1 except that a bisazo dye represented by the following general formula (V) was used instead of the bisazo dye represented by the chemical formula (IV). did.

[0045]

[Chemical 7]

On the charge generation layer thus obtained,
6 parts of an exemplified compound (compound No. 1), 10 parts of a polycarbonate resin [K-1300: manufactured by Teijin Chemicals Ltd.], 0.002 parts of methylphenylsilicone [KF50-100 cps: manufactured by Shin-Etsu Chemical Co., Ltd.], and A coating liquid consisting of 94 parts of tetrahydrofuran was prepared, and a charge transport layer having a film thickness after drying of 20.0 μm was formed in the same manner as in Example 1, and was composed of aluminum electrode / charge generation layer / charge transport layer. A laminated electrophotographic photosensitive member (photosensitive member No. 9) was prepared.

Examples 9 to 17 Instead of the exemplified compound (Compound No. 1) of Example 8, compound No. 2, compound No. 19 and compound N in the exemplified compound were used.
o.26, compound No. 27, compound No. 42, compound No.
43, Compound No. 44, Compound No. 63, Compound No. 1
Photosensitive member No. 10, photosensitive member No. 11, photosensitive member No. 12, photosensitive member N in the same manner as in Example 8 except that 13 is used.
No. 13, photoconductor No. 14, photoconductor No. 15, photoconductor No.
16, photoconductor No. 17, photoconductor No. 18, photoconductor No. 1
9 was created. Comparative Example 2 A photoconductor No. 20 was prepared in the same manner as in Example 8 except that 2,4,7-trinitrofluorenone was used in place of the exemplified compound of Example 8.

Example 18 Trisazo dye 6 represented by the following general formula (VI) was used in place of 5 parts of the bisazo dye represented by the above chemical formula (IV).
A charge generation layer was prepared in the same manner as in Production Example 1 for electrophotographic photosensitive member except that parts were used.

[0049]

[Chemical 8]

On the charge generation layer thus obtained,
6 parts of an exemplified compound (compound No. 2), 10 parts of a polycarbonate resin [K-1300: manufactured by Teijin Chemicals Ltd.], 0.002 parts of methylphenylsilicone [KF50-100 cps: manufactured by Shin-Etsu Chemical Co., Ltd.], and A coating liquid consisting of 94 parts of tetrahydrofuran was prepared, and a charge transport layer having a film thickness after drying of 20.0 μm was formed in the same manner as in Example 1, and was composed of aluminum electrode / charge generation layer / charge transport layer. A laminated electrophotographic photosensitive member (photosensitive member No. 21) was prepared.

Examples 19 to 20 Instead of the exemplified compound of Example 18 (Compound No. 2),
Photoreceptor No. 2 was prepared in the same manner as in Example 18 except that Compound No. 26 and Compound No. 42 in the exemplified compounds were used.
2. Photosensitive member No. 23 was prepared. Comparative Example 3 A photoreceptor No. 24 was prepared in the same manner as in Example 18, except that 2,4,7-trinitrofluorenone was used instead of the exemplified compound in Example 18. Example 21 X-type metal-free phthalocyanine [Fastogen Blu
e 8120BS manufactured by DIC], polyvinyl butyral resin [S-Rex BLS manufactured by Sekisui Chemical Co., Ltd.] 5
Parts and 90 parts of tetrahydrofuran in a ball mill 1
Dispersion was carried out for 2 hours, and then tetrahydrofuran was added so as to have a dispersion liquid concentration of 2% by weight and redispersed to prepare a coating liquid. The coating solution thus prepared was cast-coated with a doctor blade on a 100 μm-thick polyester film on which aluminum was vapor-deposited, and the film thickness after drying was 0.5.
A charge generation layer of μm was formed.

On the charge generation layer thus obtained,
A coating solution having a formulation consisting of 6 parts of the exemplified compound (compound No. 1), 10 parts of a polycarbonate resin [K-1300: Teijin Chemicals Ltd.], and 94 parts of tetrahydrofuran was prepared and cast-coated with a doctor blade. Then, a charge transport layer having a film thickness after drying of 20.0 μm was formed to prepare a laminated electrophotographic photoreceptor composed of an aluminum electrode / charge generation layer / charge transport layer. Examples 22 to 30 Instead of the exemplified compound of Example 21 (Compound No. 1),
Compound No. 2, Compound No. 19, Compound No. 26, Compound No. 27, Compound No. 42, Compound N in the exemplified compounds
o.43, compound No. 44, compound No. 63, compound No.
Photosensitive member No. 25, photosensitive member No. 26, photosensitive member No. 27, photosensitive member No. 28, photosensitive member No. 29, photosensitive member No. 30, in the same manner as in Example 21 except that 113 was used. Photoconductor No. 31, photoconductor No. 32, photoconductor No. 33, photoconductor N
Created o.34.

Example 31 0.5 g of the bisazo dye represented by the above chemical formula (IV) was added to 10% by weight of polycarbonate Z (manufactured by Teijin Chemicals Ltd.).
Tetrahydrofuran solution 10 g, tetrahydrofuran 9
After ball milling with g, pigment composition 2 wt%,
Polycarbonate Z composition is 50 wt%, exemplified compound (Compound No. 2) is 20 wt%, and the following hole transfer substance is 28
A 10 wt% polycarbonate Z solution, a pentadiene compound, and a hole transfer substance were added so that the wt% was obtained, and the mixture was sufficiently stirred to prepare a photoreceptor coating liquid. The coating solution thus prepared is applied onto a polyester film having a thickness of 1000 A of aluminum and having a thickness of 15 μm by applying a doctor blade onto a polyester film having a thickness of 75 μm. Photosensitive member No. 35 was prepared.

[0054]

[Chemical 9]

Examples 32 to 36 Instead of the exemplified compound of Example 31 (Compound No. 2),
Photoreceptor No. 3 was prepared in the same manner as in Example 31 except that Compound No. 19, Compound No. 26, Compound No. 27, Compound No. 42 and Compound No. 43 in the exemplified compounds were used.
6, photoconductor No.37, photoconductor No.38, photoconductor No.3
9. Photoconductor No. 40 was prepared.

Comparative Example 4 Photosensitive member No. 41 was prepared under the same conditions as in Example 32 except that the pentadiene compound was omitted. Example 37 After 0.5 g of metal-free phthalocyanine was ball-milled with 10 g of a 10 wt% tetrahydrofuran solution of polycarbonate Z and 9 g of tetrahydrofuran, the pigment composition was 2 wt%, the polycarbonate Z composition was 50 wt%, and the exemplified compound (Compound No. 2) was 20 wt%. A 10 wt% polycarbonate Z solution, a pentadiene compound, and a hole-transporting substance were added so that the following hole-transporting substance would be 28 wt%, and the mixture was sufficiently stirred to prepare a photoreceptor coating liquid. The coating solution thus prepared is applied onto a polyester film having a thickness of 1000 A of aluminum and having a thickness of 15 μm by applying a doctor blade onto a polyester film having a thickness of 75 μm. A photoconductor No. 42 was prepared.

[0057]

[Chemical 10]

Examples 38 to 42 Instead of the exemplified compound of Example 37 (Compound No. 2),
Photoreceptor No. 4 was prepared in the same manner as in Example 37 except that Compound No. 19, Compound No. 26, Compound No. 27, Compound No. 42 and Compound No. 43 in the exemplified compounds were used.
3, photoconductor No.44, photoconductor No.45, photoconductor No.4
6. Photosensitive member No. 47 was prepared.

Comparative Example 5 A photoconductor No. 48 was prepared under the same conditions as in Example 38 except that the pentadiene compound was omitted. The characteristics of the electrophotographic photosensitive member obtained as described above were evaluated as follows using an electrostatic copying paper test apparatus (Kawaguchi Denki Seisakusho: SP-428). Apply + 6KV corona discharge,
After being positively charged, it is left in a dark place for 20 seconds, the surface potential V _o at that time is measured, and then light irradiation is performed using a tungsten lamp so that the illuminance on the surface becomes 20 lux, at which time V _o is halved. The exposure amount required to become E _1/2 (lux.
sec) was measured. The results are shown in Tables 2-7.

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

[0063]

[Table 16]

[0064]

[Table 17]

[0065]

[Table 18]

[0066]

The cyclopentadiene compound represented by the general formula (I) according to the present invention is novel, can be produced by a relatively simple and efficient method, and has excellent solubility or dispersion in a binder resin. And has an excellent ability to receive and transport the charge generated by the charge generating substance, and has an excellent function as a charge transporting substance.
Further, the electrophotographic photosensitive member of the present invention containing these cyclopentadiene compound as a charge transporting material has a high dark decay rate and a high sensitivity and is excellent in durability.

[Brief description of drawings]

FIG. 1 is a sectional view of an electrophotographic photosensitive member according to the present invention.

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

FIG. 3 is a cross-sectional view of still another example of an electrophotographic photosensitive member according to the present invention.

FIG. 4 is an infrared absorption spectrum diagram of the cyclopentadiene compound represented by Structural Formula (42) obtained in Synthesis Example 1.

5 is an infrared absorption spectrum diagram of the cyclopentadiene compound represented by Structural Formula (43) obtained in Synthesis Example 2. FIG.

[Explanation of symbols]

 1 Support 2 Charge Generation Layer 3 Charge Transport Layer 4 Photosensitive Layer (Layered Structure) 5 Protective Layer 6 Photosensitive Layer (Single Layered Structure)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 69/734 Z 9546-4H 69/738 Z 9546-4H 69/757 Z 9546-4H 69/76 A 9546-4H 205/45 7537-4H 251/20 255/45 G03G 5/06 313 (72) Inventor Akio Kojima 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd.

Claims (4)

[Claims] 1. A cyclopentadiene compound represented by the following general formula (I): [Chemical 1] [Wherein R ₁ and R ₄ are the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted alkoxycarbonyl groups] Represents a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted acyl group, a cyano group, a nitro group or at least one group selected from the group consisting of halogen atoms. R ₂ and R ₃ are at least one group selected from the group consisting of the same or different hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic groups, and substituted or unsubstituted heterocyclic groups. Represents X represents ═O and at least one group selected from the group consisting of groups represented by the following formulas (II) and (III). = C (A) (B) (II) = NR- ₅ (III) (In the above (II), A and B are the same or different hydrogen atom, halogen atom, cyano group, substituted or unsubstituted aromatic group. And at least one group selected from the group consisting of —COOR _{6. In the} above (III), R ₅
Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, or a cyano group. R ₆ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group. )] 2. An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer formed thereon as an essential component, and the photosensitive layer containing a cyclopentadiene compound represented by formula (I). [Chemical 2] In [the above formula _{(I), R 1, R} 2, R 3, R 4 and X have the same meanings as _{R 1, R 2, R 3} , R 4 and X in claim 1. ] 3. The electrophotography according to claim 2, wherein the photosensitive layer comprises two layers of a charge generation layer and a charge transport layer, and at least the charge transport layer contains the cyclopentadiene compound represented by the general formula (I). Photoconductor. 4. A single-layer type electrophotographic photoreceptor in which the photosensitive layer contains a charge generating substance and a charge transporting substance, and contains at least one cyclopentadiene compound represented by the general formula (I) as a charge transporting substance. Item 2. The electrophotographic photosensitive member according to item 2.