JP2000219657A - Stilbene derivative, its production and electrophotographic photoreceptor containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound comprising a specific stilbene derivative, having excellent compatibility with a binder resin and a high charge mobility, useful as a charge transporting agent for electrophotographic photoreceptor. SOLUTION: This compound is shown by formula [R1 and R3 are each a (substituted)alkyl or the like, and R2 and R4 are each a (substituted)alkoxy or the like]. The compound of formula I is obtained by reacting a formylated triphenylamine derivative of formula II with a bisphosphoric ester derivative of formula III in an anhydrous solvent (e.g. diethyl ether) in the presence of a base (e.g. sodium methoxide) at -10 to 25 deg.C for 3-12 hours. The amount of the base used is preferably 2-2.5 times as much as the molar amount of the compound of formula III. The amount of the compound of formula II used is preferably 1.95-2.05 times as much as the molar amount. The compound of formula II is obtained by reacting an aniline of formula IV with an aniline derivative of formula IV with iodobenzene to give a triphenylamine derivative of formula V and formylating the compound by a Vilsmeier method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solar cell, for example,
The present invention relates to a novel stilbene derivative suitably used as a charge transporting agent (in particular, a hole transporting agent) in an electroluminescence element, an electrophotographic photoreceptor, and the like, a method for producing the same, and an electrophotographic photoreceptor using the same.

[0002]

2. Description of the Related Art In an image forming apparatus, various organic photoconductors having sensitivity in a wavelength region of a light source used in the apparatus are used. This organic photoreceptor is easier to manufacture than conventional inorganic photoreceptors, has a wide variety of photoreceptor materials such as charge transport agents, charge generators, and binder resins, and has a high degree of freedom in functional design. In recent years, because of its advantages,
Widely used.

[0003] The organic photoreceptor includes a single-layer type photoreceptor in which a charge transporting agent and a charge generating agent are dispersed in the same photosensitive layer.
There is a laminated photoreceptor in which a charge generating layer containing a charge generating agent and a charge transporting layer containing a charge transporting agent are laminated. Generally, since the organic photoreceptor does not have a film-forming ability, it is used by being incorporated in a suitable binder, for example, a resin. As a charge transporting agent used in the above-mentioned organic photoreceptor, JP-A-50
JP-A-31773 and JP-A-2-154268 disclose stilbene derivatives.

[0004]

However, the stilbene derivatives disclosed in the above publications generally have poor compatibility with the binder resin, are not uniformly dispersed in the photosensitive layer, and are unlikely to cause charge transfer. Therefore, despite the fact that the stilbene derivative itself has a high charge mobility, when it is used in a photoreceptor as a charge transporting agent, its characteristics cannot be sufficiently exhibited, and the residual potential of the photoreceptor is not sufficient. And the light sensitivity was not sufficient.

A main object of the present invention is to solve the above technical problems and to provide a novel stilbene derivative suitable as a charge transporting agent for an electrophotographic photoreceptor and a method for producing the same. Another object of the present invention is to provide an electrophotographic photoreceptor having improved sensitivity as compared with the related art.

[0006]

Means for Solving the Problems As the inventors of the present invention have continued to study to solve the above-mentioned problems, among the stilbene derivatives, they are compounds in which the diphenylamino group at the molecular terminal is asymmetric, and in particular, A stilbene derivative represented by the following general formula (1), wherein one of the phenyl groups in the diphenylamino group has no substituent, and the other phenyl group has one substituent at the 2-position and another arbitrary position. Have found a new fact that they have better compatibility with a binder resin and higher charge mobility than conventional stilbene derivatives, and have completed the present invention.

That is, the stilbene derivative of the present invention is
General formula (1):

[0008]

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(In the formula, R ¹ and R ³ are the same or different, and may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. An aryl group or an alkoxy group which may have a substituent, R ² and R ⁴ are the same or different and an alkyl group which may have a substituent or an alkoxy group which may have a substituent; ).

The stilbene derivative (1) has cis and trans isomers because it has three —CH 、 CH— groups in its structure, but the present invention includes both of them. is there. The stilbene derivative of the present invention represented by the above general formula (1) is disclosed in the above-mentioned JP-A-50-3177.
No. 3 and the compound not specifically disclosed in JP-A-2-154268, the compatibility with the binder resin is higher than the compounds specifically disclosed in the above-mentioned publication, and the charge mobility is higher. Since the stilbene derivative (1) is large, the use of the stilbene derivative (1) as a charge (hole) transport agent in an electrophotographic photoreceptor can provide a high-sensitivity electrophotographic photoreceptor.

The present inventors have studied a method for efficiently obtaining the following formyl form of triphenylamine (2), which is a starting material, in the method for producing the stilbene derivative (1). Is substituted with a triphenylamine derivative (5) by Vilsmeier (Vil
smeier), the compound (5)
Of the three phenyl groups in the above, the phenyl group having a substituent is not formylated, and the compound (2) in which only the unsubstituted phenyl group is formylated can be efficiently produced,
The present inventors have found a new fact that the productivity of the stilbene derivative (1) is improved, and have completed the present invention.

That is, the method for producing the stilbene derivative (1) of the present invention is represented by the general formula (2):

[0013]

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(Wherein R ¹ represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. have a alkoxy group optionally, R ² is formylated triphenylamine derivative represented by the.) showing the alkoxy group which may have also an alkyl group or a substituent substituted And the general formula (3):

[0015]

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And reacting the bisphosphate ester derivative represented by the formula (1). The formylated triphenylamine derivative (2) used in the production method of the present invention has the general formula (4):

[0017]

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(Wherein R ¹ represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. the which may have an alkoxy group, R ² is a iodobenzene aniline derivative represented by the.) showing the alkoxy group which may have an optionally substituted alkyl group or a substituted group And reacting with the general formula (5):

[0019]

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(Wherein, R ¹ represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. R ² represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent.) Is a compound obtained by subjecting this compound (5) to formylation by the Vilsmeier method.

When the triphenylamine derivative (5) is formylated by the Vilsmeier method, only the formyl derivative (2) of triphenylamine, which is a raw material of the stilbene derivative (1), is produced in high yield. Although it is not clear, among the three phenyl groups in the compound (5), a phenyl group having a substituent R ¹ in the ortho position is
Compared with the other phenyl groups, the bond axis between the nitrogen atom and the phenyl group in the compound (5) is twisted by the influence of the substituent R ¹ , and the electron donation from the nitrogen atom becomes poor, and the nucleophilicity of the phenyl group is reduced. Decrease. As a result, it is presumed that the para position of the phenyl group is not formylated and only the para position of the other phenyl group is formylated.

Next, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer comprises a stilbene derivative represented by the general formula (1). It is characterized by containing. Since the electrophotographic photoreceptor of the present invention contains the stilbene derivative represented by the general formula (1) in the photosensitive layer, the speed of transporting the charges (holes) generated by the charge generating agent is high, that is, the charge is high. It has high mobility and excellent light sensitivity during charging and exposure. As a result, according to the electrophotographic photoreceptor of the present invention, higher sensitivity can be obtained than when a conventional stilbene derivative is used as a hole transporting agent.

The photosensitive layer is preferably a single-layer photosensitive layer containing a stilbene derivative represented by the general formula (1), a charge generating agent and an electron transporting agent.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Stilbene Derivative] In the stilbene derivative represented by the general formula (1), examples of the alkyl group corresponding to R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, s
And C1-C6 groups such as -butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl and the like. Among them, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-
An alkyl group having 1 to 4 carbon atoms such as butyl is preferred.

The alkyl groups corresponding to R ¹ , R ² , R ³ and R ⁴ may have a substituent. Specifically, a hydroxyl group, an alkoxyalkyl group, an alkylaminoalkyl group, a dialkylamino Examples thereof include an alkyl group, a halogenated alkyl group, an alkoxycarbonylcarbonylalkyl group, a carboxyalkyl group, an alkanoyloxyalkyl group, and an aminoalkyl group. In particular, in the stilbene derivative (1) of the present invention, an alkyl group having an electron-donating group such as an alkoxy group, an amino group, an alkylamino group, or a dialkylamino group is preferable from the viewpoint of increasing charge mobility.

Examples of the above hydroxyl group include hydroxymethyl, 2-hydroxymethyl, 1,1-dimethyl-2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypropyl, 2-hydroxypropyl, 1-hydroxypentyl and And hydroxyalkyl having 1 to 6 carbon atoms in the alkyl moiety, such as -hydroxyhexyl.

Examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl, methoxybutyl,
Ethoxyhexyl, ethoxymethyl, butoxyethyl,
Examples thereof include alkoxyalkyl groups in which the alkyl portion and the alkoxy portion each have 1 to 6 carbon atoms, such as t-butoxyhexyl and hexyloxymethyl.
Examples of the alkylaminoalkyl group include methylaminomethyl, ethylaminomethyl, hexylaminomethyl, ethylaminoethyl, hexylaminoethyl, methylaminopropyl, butylaminopropyl, methylaminobutyl, ethylaminobutyl, hexylaminobutyl, methyl Examples thereof include an alkylaminoalkyl group having 1 to 6 carbon atoms in the alkyl moiety, such as aminohexyl, ethylaminohexyl, butylaminohexyl, or hexylaminohexyl.

Examples of the above dialkylaminoalkyl groups include dimethylaminomethyl, diethylaminomethyl, dihexylaminomethyl, diethylaminoethyl,
The alkyl moiety has 1 to 6 carbon atoms, such as dihexylaminoethyl, diethylaminopropyl, dibutylaminopropyl, dimethylaminobutyl, diethylaminobutyl, dihexylaminobutyl, dimethylaminohexyl, diethylaminohexyl, dibutylaminohexyl or dihexylaminohexyl. And dialkylaminoalkyl groups.

Examples of the above alkoxycarbonylalkyl group include methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylhexyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, pentyloxycarbonylmethyl, Examples thereof include an alkoxycarbonyl group such as hexylcarbonylmethyl, hexylcarbonylbutyl or hexylcarbonylhexyl, in which both the alkyl portion and the alkoxy portion have 1 to 6 carbon atoms.

Examples of the carboxyalkyl group include carboxyalkyl groups having 1 to 6 carbon atoms in the alkyl moiety, such as carboxymethyl, carboxyethyl, carboxybutyl, carboxyhexyl and 1-methyl-2-carboxyethyl. . Examples of the halogenated alkyl group include, for example, monochloromethyl, monobromomethyl, monoiodomethyl, monofluoromethyl, dichloromethyl, dibromomethyl, diiodomethyl, difluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, trifluoromethyl, monochloro Ethyl, monobromoethyl, monoiodoethyl,
1 such as monofluoroethyl, dibromobutyl, diiodobutyl, difluorobutyl, chlorhexyl, bromohexyl, iodohexyl or fluorohexyl;
And an alkyl group having 1 to 6 carbon atoms substituted with up to 3 halogen atoms.

The alkanoyloxyalkyl group includes acetoxymethyl, 2-acetoxyethyl, propionyloxymethyl or 1-hexanoyloxy-2
Alkanoyloxy groups having an alkanoyl moiety having 2 to 6 carbon atoms and an alkyl moiety having 1 to 6 carbon atoms, such as -methylpentyl. Examples of the aminoalkyl group include an aminoalkyl group having an alkyl portion having 1 to 6 carbon atoms, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl or aminohexyl.

Examples of the alkoxy group corresponding to R ¹ , R ² , R ³ and R ⁴ include methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy, hexyloxy and the like. And 6 alkoxy groups. The alkoxy group corresponding to R ¹ , R ² , R ³ and R ⁴ may have a substituent, and the substituent includes a halogen atom, an amino group,
Examples include the same substituents as in the alkyl group described above, such as a hydroxyl group, a carboxyl group or an alkanoyloxy group.

Aryl corresponding to R ¹ and R ²
Examples of the group include groups such as phenyl, naphthyl, anthryl, and phenanthryl. Examples of the aralkyl group corresponding to R ¹ and R ² include benzyl, 1-phenylethyl, 3-phenylpropyl,
An aralkyl group having 1 to 6 carbon atoms in the alkyl moiety such as phenylbutyl, 5-phenylpentyl or 6-phenylhexyl is exemplified.

The aryl group and the aralkyl group may have a substituent. Examples of the substituent include a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified and a cyano group. In addition to the groups and the like, there may be mentioned the same alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms as described above. These substitution positions are not particularly limited.

The stilbene derivative (1) of the present invention includes the following general formulas (11) to (13) depending on the substitution position on the central stilbene ring group, and particularly includes the general formulas (11) and (12). The stilbene derivative represented by) is preferred.

[0036]

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(Wherein, R ^{1 to} R ⁴ have the same meanings as described above.) As specific examples of the stilbene derivative represented by the general formula (1), substituents corresponding to the groups R ^{1 to} R ⁴ are shown below. Are shown in Tables 1 to 3. In Tables 1 to 3, compounds having a compound number starting with "11-" are stilbene derivatives contained in the general formula (11),
Compound numbers starting with "12-" are represented by the general formula (12)
Wherein the compound number starts with "13-" is a stilbene derivative included in the general formula (13). In Tables 1 to 3, H is a hydrogen atom, Me is a methyl group, Et is an ethyl group, i-Pr is an isopropyl group, t-Bu is a tertiary-butyl group, and s-Bu.
Represents a secondary-butyl group, Ph represents a phenyl group, and Bzl represents a benzyl group.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[Method for Producing Stilbene Derivative] The method for synthesizing the stilbene derivative (1) of the present invention will be described by taking, as an example, a case where R ¹ and R ³ are the same group and R ² and R ⁴ are the same group. explain. Reaction formula (I):

[0042]

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(Wherein R ¹ and R ⁴ have the same meanings as described above.) In this reaction, the formyl form of triphenylamine represented by the general formula (2) and the bisphosphate ester derivative (3) are reacted. The reaction is carried out in a suitable anhydrous solvent in the presence of a base, whereby the stilbene derivative of the present invention represented by the general formula (1-a) is obtained.

The solvent used in the above reaction is not particularly limited as long as it does not affect the reaction itself. Examples thereof include ethers such as diethyl ether, tetrahydrofuran and dioxane; and halogenated compounds such as methylene chloride, chloroform and dichloroethane. Hydrocarbons include aromatic hydrocarbons such as benzene and toluene. Examples of the base include sodium alkoxides such as sodium methoxide and metal hydrides such as sodium hydride.

The amount of the base used relative to the bisphosphate ester derivative of the general formula (3) is at least 2 to 4 moles,
Preferably it is 2-2.5 times molar amount. The amount of the compound (2) used is 1.8 relative to the phosphate ester derivative (3).
The molar amount is up to 2.5 times, preferably 1.95 to 2.05 times. The reaction is usually performed at −10 to 25 ° C.
It ends in about 12 hours.

Reaction formula (II):

[0047]

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(In the formula, R ¹ and R ² have the same meanings as described above.) In this reaction, an aniline derivative (4) and iodobenzene (90) are added to nitrobenzene, and anhydrous potassium carbonate, copper or the like is added. By reacting with the catalyst, a triphenylamine derivative (5) is obtained. Then, the triphenylamine derivative (5) is formylated by the Vilsmeier method to obtain trimethylamine derivative (5), which is a starting material of the above reaction formula (1). A phenylamine formyl compound (2) is obtained.

The aniline derivative (4) and iodobenzene (90) were used in a molar ratio of 1: 1.7-3,
Preferably it is 1: 1.8-2.2. The reaction is usually 1
The reaction is performed at 60 to 220 ° C., and is completed in about 4 to 30 hours. Reagents used in the Vilsmeyer method (Vilsmeie
r reagent) includes (i) a halogenating agent such as phosphorus oxychloride, phosgene, oxalyl chloride, thionyl chloride, triphenylphosphine-bromine, hexachlorotriphosphazatriene, and (ii) N, N-dimethylformamide (DM
F), prepared by a combination with N-methylformanilide (MFA), N-formylmorpholine, N, N-diisopropylformamide and the like. In particular, in the present invention,
A combination of phosphorus oxychloride and DMF, which can also be used as a solvent, is preferably used.

In the preparation of the Vilsmeier reagent, the use ratio of (i) and (ii) is usually 1: 1 to 1 in molar ratio.
2, preferably 1: 1 to 1.2. The amount of the Vilsmeier reagent to be used is 0.9 to 2 times, preferably 1 to 1.1 times, the molar amount of the triphenylamine derivative (5). The formylation of the compound (5) is usually carried out at 40
It is carried out at ~ 80 ° C and is completed in about 2-5 hours.

In the stilbene derivative (1) of the present invention, when synthesizing an alkyl group in which R ¹ and / or R ² has a substituent, for example, a stilbene derivative in which R ¹ is a hydroxylalkyl group, Or a stilbene derivative in which R ¹ is an alkyl group, and then converting the alkyl group to a hydroxylalkyl group by a conventional method (eg, oxidation). Good.

Reaction formula (III):

[0053]

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(In the formula, X represents a halogen atom.) This reaction is carried out by reacting bishalogenomethylstilbene (91) with a phosphite triester in a solvent-free or suitable solvent. Bisphosphate ester derivative (3) which is a starting material of (1) is obtained. At that time, when a tertiary amine is added, the alkyl halide is removed from the reaction system, and the reaction is accelerated.

The solvent used in the above reaction may be any solvent which does not affect the reaction, and examples thereof include ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; benzene. , Toluene and other aromatic hydrocarbons, and dimethylformamide. Examples of the tertiary amine include triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine and the like.

The use amount of the phosphite triester to the bishalogenomethylstilbene (91) is at least 2
The molar amount is preferably 2 to 2.4 times the molar amount. The reaction is usually performed at 80 to 150 ° C., and is completed in about 1 to 4 hours. Reaction formula (IV):

[0057]

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(Wherein, R and R ′ are the same or different and each represent an alkyl group having 1 to 6 carbon atoms, and X has the same meaning as described above.) This reaction is carried out using a halogenated methyl benzoic acid (97) Is subjected to an esterification reaction, and the obtained ester (98) is reacted with trister phosphite to obtain a monophosphate derivative (99), and then reacted with an aldehyde benzoate to obtain a stilbene dicarboxylate (100). This compound is subjected to a reduction reaction to prepare stilbenedihydroxymethyl (101), and then reacted with a halogenating agent to obtain a compound (91) which is a starting material of the reaction step formula (III). Things.

The above esterification reaction is carried out, for example, by reacting a methyl benzoic acid (97) in the presence of a catalyst with the general formula: R
The reaction is carried out by reacting an alcohol represented by -OH (wherein R is as defined above). As a catalyst to be used, a catalyst commonly used for an esterification reaction is used, and specifically, inorganic acids such as hydrogen chloride, concentrated sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride, perchloric acid, and trifluoroacetic acid , Organic acids such as trichloromethanesulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid and ethanesulfonic acid, acid anhydrides such as trichloromethanesulfonic anhydride and trifluoromethanesulfonic acid, and catalysts such as thionyl chloride Is raised.

The above esterification reaction is carried out without a solvent or in the presence of a suitable catalyst. As the solvent, any solvent can be used as long as it is a solvent commonly used in esterification reactions, for example, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane and chloroform, and diethyl ether. And ethers such as tetrahydrofuran and dioxane.

The proportion of the alcohol to the compound (97) is 1 to 3 moles, preferably 1.5 to 2.0 moles.
The amount is preferably twice as much. The reaction temperature is 80 to 16
It is good to carry out at 0 ° C, preferably at 100 to 150 ° C. The reaction for obtaining the compound (99) from the compound (98) is carried out without a solvent or in a suitable solvent. At that time, when a tertiary amine is added, the alkyl halide is removed from the reaction system, and the reaction is accelerated. .

The solvent used in the above reaction may be any solvent which does not affect the reaction, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; benzene, Examples thereof include aromatic hydrocarbons such as toluene and dimethylformamide. Examples of the tertiary amine include triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine and the like.

The amount of the phosphite triester to be used relative to the compound (98) is at least equimolar, preferably from 1 to
1.2 times the molar amount. The reaction is usually performed at 80 to 150 ° C.
And is completed in about 1 to 4 hours. Compound (9
The reaction for obtaining the compound (100) from 9) can be carried out according to the above-mentioned reaction formula (1). Here, the amount of the base to be used is at least 1 to 2 times, preferably 1 to 1.3 times the molar amount of the phosphate derivative of the compound (99). The amount of compound (99a) used is the same as that of compound (9)
0.9 to 1.3 times the molar amount of 9), preferably 0.1 mol.
It is 98 to 1.02 times the molar amount. The reaction is usually -10
The reaction is performed at ２５25 ° C. and is completed in about 3 to 10 hours.

The reaction for obtaining the compound (101) from the compound (100) is carried out in a suitable solvent. Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran, dioxane, and diglyme; aliphatic hydrocarbons such as hexane and heptane; and aromatic hydrocarbons such as benzene and toluene. The hydride reducing agent used in this reaction includes lithium aluminum hydride, aluminum hydride, diisopropyl aluminum hydride,
Examples include lithium borohydride, sodium borohydride-aluminum chloride, diborane and the like. Compound (10
The amount of the hydride reducing agent to be used with respect to 0) is at least twice the molar amount, preferably about 2 to 2.2 times the molar amount. The reaction is usually carried out under ice cooling to 120 ° C, preferably 30 ° C.
Performed at 80 ° C. and ends in about 1-20 hours.

The reaction for obtaining the compound (91) from the compound (101) is carried out without a solvent or in a suitable solvent. Examples of the solvent used in this reaction include ethers such as diethyl ether, tetrahydrofuran, and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane; and aromatic hydrocarbons such as benzene and toluene. This reaction is preferably performed in the presence of a catalyst, such as pyridine, DMF, picoline,
HMPA and the like.

Examples of the halogenating agent used in this reaction include, for example, hydrogen halides such as thionyl chloride, thionyl bromide, hydrogen chloride, hydrogen bromide and hydrogen iodide, phosphorus trichloride, phosphorus tribromide and the like. And phosphorus halides. The amount of the halogenating agent to be used is at least 2 times, preferably 2 to 5 times, the molar amount of the compound (99). The reaction is carried out under ice-cooling to 120 ° C, preferably about 40-100 ° C, and is completed in about 1-18 hours.

Next, in the synthesis of the stilbene derivative,
When the groups R ¹ and R ³ or R ² and R ⁴ are different groups,
It is synthesized by sequentially reacting a monophosphate derivative instead of the phosphate derivative of the general formula (3) with a formyl derivative (2) of triphenylamine having a different group. Specifically, as shown in the following reaction formula (IV), first, a compound of the formula (92) is reacted with a phosphite triester to obtain a monophosphate ester (93). The monostilbene derivative (94) is reacted by reacting the formyl compound (2) of the amine to obtain a compound (95) obtained by chlorinating the monostilbene derivative (94).

Reaction formula (IV):

[0069]

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(Wherein X, R ¹ and R ² are as defined above). Then, as shown in the following reaction formula (V), the compound (9)
5) is reacted with phosphite triester to give compound (9).
6), and the stilbene derivative is reacted with a formyl derivative of triphenylamine (2 ′).
(1 ′) is obtained. Reaction formula (V):

[0071]

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(Wherein X, R ^{1 to} R ⁴ have the same meanings as described above.) As described above, the stilbene derivative represented by the general formula (1) has a large charge mobility, that is, a high hole. Since it has a transporting property, it can be suitably used as a hole transporting agent in an electrophotographic photoreceptor, and can be used in various fields such as a solar cell and an electroluminescent device. Next, the electrophotographic photosensitive member of the present invention will be described in detail.
The electrophotographic photoreceptor of the present invention has a photosensitive layer containing a stilbene derivative represented by the general formula (1) provided on a conductive substrate. As described above, there are a single-layer type and a stacked-type photoreceptor, and the present invention can be applied to any of them.

The single-layer type photoreceptor has a single photosensitive layer provided on a conductive substrate. This photosensitive layer has the general formula (1)
The stilbene derivative represented by the formula (hole transporting agent), a charge generating agent, a binder resin, and, if necessary, an electron transporting agent are dissolved or dispersed in a suitable solvent, and the obtained coating solution is placed on a conductive substrate. It is formed by applying and drying. Such a single-layer type photoreceptor can be applied to both positive and negative charging types in a single configuration, and has a simple layer configuration and excellent productivity.

The single-layer type electrophotographic photoreceptor of the present invention has a much lower residual potential and a higher sensitivity than the conventional single-layer type electrophotographic photoreceptor. On the other hand, in the laminated photoreceptor, first, a charge generation layer containing a charge generation agent is formed on a conductive substrate by means such as vapor deposition or coating, and then, on the charge generation layer, a general formula (1) is used. The charge transport layer is formed by applying a coating solution containing at least one of the represented stilbene derivatives (hole transporting agents) and a binder resin, followed by drying to form a charge transport layer. Conversely, a charge transport layer may be formed on a conductive substrate, and a charge generation layer may be formed thereon. However, since the charge generation layer is very thin compared to the charge transport layer, it is preferable to form the charge generation layer on a conductive substrate and to form the charge transport layer thereon for protection. .

Depending on the order of forming the charge generation layer and the charge transport layer and the type of the charge transport agent used in the charge transport layer, the positive or negative charge type of the laminated type photoreceptor is selected. For example, as described above, when a charge generation layer is formed on a conductive substrate and a charge transport layer is formed thereon, the stilbene derivative (1) of the present invention may be used as a charge transport agent in the charge transport layer. When a suitable hole transporting agent is used, the photoconductor becomes negatively charged.

The laminated electrophotographic photoreceptor of the present invention has significantly lower residual potential of the photoreceptor than the conventional laminated electrophotographic photoreceptor using a stilbene derivative as a hole transporting agent, and has a lower sensitivity. Has improved. As described above, the electrophotographic photoreceptor of the present invention can be applied to any of a single-layer type and a laminated type, but can be used for both positive and negative charging types, and has a simple structure and is easy to manufacture. The single-layer type is preferred from the viewpoints that film defects at the time of forming the layer can be suppressed, the interface between the layers is small, and the optical characteristics can be improved.

Next, various materials used for the electrophotographic photosensitive member of the present invention will be described. << Charge Generating Agent >> Examples of the charge generating agent used in the present invention include compounds represented by the following general formulas (CG1) to (CG12). (CG1) Metal-free phthalocyanine

[0078]

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(CG2) oxotitanyl phthalocyanine

[0080]

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(CG3) Perylene pigment

[0082]

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(Wherein R ^g1 and R ^g2 are the same or different and represent a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, alkanoyl group or aralkyl group having 18 or less carbon atoms) (CG4 ) Bisazo pigment

[0084]

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[Wherein C ^P1 and C ^P2 are the same or different and represent a coupler residue, and Q represents the following formula:

[0086]

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(Wherein, R ^g3 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group or the heterocyclic group may have a substituent.
Represents 0 or 1. )

[0088]

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(In the formula, R ^g4 and R ^g5 are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group.)

[0090]

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(In the formula, R ^g6 represents a hydrogen atom, an ethyl group, a chloroethyl group or a hydroxyethyl group.)

[0092]

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Or

[0094]

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( ^Wherein R ^g7 , R ^g8 and R ^g9 are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group, an aryl group or an aralkyl group). Shows the group to be formed. (CG5) dithioketopyrrolopyrrole pigment

[0096]

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^Wherein R ^g10 and R ^g11 are the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ^g12 and R ^g13 are the same or different and represent a hydrogen atom, an alkyl group or an aryl group. (CG6) Metal-free naphthalocyanine pigment

[0098]

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^Wherein R ^g14 , R ^g15 , R ^g16 and R ^g17
Represents the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. (CG7) Metal naphthalocyanine pigment

[0100]

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^Wherein R ^g18 , R ^g19 , R ^g20 and R ^g21
Is the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and M represents Ti or V. ) (CG8) Squaraine pigment

[0102]

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( ^Wherein R ^g22 and R ^g23 are the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom.) (CG9) Trisazo pigment

[0104]

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(Wherein C ^P3 , C ^P4 and C ^P5 are the same or different and represent a coupler residue.) (CG10) Indigo pigment

[0106]

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(In the formula, R ^g24 and R ^g25 are the same or different and each represent a hydrogen atom, an alkyl group or an aryl group, and Z represents an oxygen atom or a sulfur atom.) (CG11) Azulhenium pigment

[0108]

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( ^Wherein R ^g26 and R ^g27 are the same or different and each represent a hydrogen atom, an alkyl group or an aryl group.) (CG12) Cyanine pigment

[0110]

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( ^Wherein , R ^g28 and R ^g29 are the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ^g30 and R ^g31 are the same or different and represent a hydrogen atom, an alkyl group or an aryl group. Represents a group.) In the above-described charge generating agent, as the alkyl group,
In addition to the groups described above, groups having 5 to 6 carbon atoms such as n-pentyl and n-hexyl are included. The substituted or unsubstituted alkyl group having 18 or less carbon atoms is a group containing heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, pentadecyl, octadecyl and the like in addition to the alkyl group having 1 to 6 carbon atoms.

Examples of the cycloalkyl group include those having 3 to 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
And 8 groups. Examples of the alkoxy group include groups having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, n-pentyloxy, and n-hexyloxy.

Examples of the aryl group include phenyl, naphthyl, anthryl, phenanthryl and the like. Examples of the alkanoyl group include formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl and the like. As the halogen atom, fluorine,
Chlorine, bromine and iodine. Heterocyclic groups include, for example, thienyl, furyl, pyrrolyl, pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, 2H-imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyranyl, pyridyl, piperidyl, piperidino, 3-morpholinyl,
Morpholino, thiazolyl and the like. Further, it may be a heterocyclic group condensed with an aromatic ring.

The substituents which may be substituted on the above groups include:
For example, a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms which may have an aryl group And 6 alkenyl groups. Examples of the coupler residues represented by C ^P1 , C ^P2 , C ^P3 , C ^P4 and C ^P5 include, for example, compounds represented by the following general formula (Cp-1):
The groups shown in (Cp-11) can be mentioned.

[0115]

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[0116]

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In each formula, R ^g32 represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group or a succinamoyl group. These groups include a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a nitro group, a cyano group, an alkyl group, an alkenyl group,
It may have a substituent such as a carbonyl group or a carboxyl group.

R ^g33 represents an atomic group necessary for forming an aromatic ring, a polycyclic hydrocarbon or a heterocyclic ring by condensing with a benzene ring, and these rings have the same substituents as described above. You may. R ^g34 represents an oxygen atom, a sulfur atom or an imino group. R ^g35 represents a divalent chain hydrocarbon group or an aromatic hydrocarbon group, and these groups may have the same substituent as described above.

R ^g36 represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituent as described above. R ^g37 is required to form a heterocyclic ring together with a divalent chain hydrocarbon group or an aromatic hydrocarbon group, or with two nitrogen atoms in the above groups (Cp-1) to (Cp-11). Represents an atomic group, and these rings may have the same substituents as described above.

R ^g38 represents a hydrogen atom, an alkyl group, an amino group, a carbamoyl group, a sulfamoyl group, an allophanoyl group, a carboxyl group, an alkoxycarbonyl group, an aryl group or a cyano group, and the groups other than the hydrogen atom are the same as those described above. It may have a substituent. R ^g39 represents an alkyl group or an aryl group, and these groups may have the same substituent as described above.

Examples of the alkenyl group include those having 2 to 2 carbon atoms such as vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, 2-pentenyl and 2-hexenyl.
And 6 alkenyl groups. In the above R ^g33 ,
Examples of the atomic group necessary to form an aromatic ring by condensing with a benzene ring include an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, trimethylene, and tetramethylene.

The aromatic ring formed by the condensation of R ^g33 with a benzene ring includes, for example, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a naphthacene ring and the like. In R ^g33 , the atomic group necessary for condensing with a benzene ring to form a polycyclic hydrocarbon includes, for example, the alkylene group having 1 to 4 carbon atoms, or a carbazole ring, a benzocarbazole ring, or a dibenzofuran ring. And the like.

In R ^g33 , the atomic groups necessary for condensing with a benzene ring to form a heterocyclic ring include, for example, benzofuranyl, benzothiophenyl, indolyl,
H-indolyl, benzoxazolyl, benzothiazolyl, 1H-indolyl, benzimidazolyl, chromenil, chromanil, isochromanyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazonyril, quinoxalinyl, dibenzofuranyl, carbazolyl, xanthenyl, acridinyl, phenanthrinyl Phenazinyl, phenoxazinyl, thianthrenyl and the like can be mentioned.

Examples of the aromatic heterocyclic group formed by condensation of R ^g33 and a benzene ring include thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, and pyridyl. And thiazolyl. Further, it may be a heterocyclic group condensed with another aromatic ring (for example, benzofuranyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolyl and the like).

In R ^g35 and R ^g37 , ^examples of the divalent chain hydrocarbon group include ethylene, trimethylene, and tetramethylene, and examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, and phenanthrylene. Is raised. In the above R ^g36 , as the heterocyclic group,
Pyridyl, pyrazyl, thienyl, pyranyl, indolyl and the like.

In R ^g37 , ^examples of the atomic group necessary for forming a heterocyclic ring with two nitrogen atoms include phenylene, naphthylene, phenanthrylene, ethylene, trimethylene, and tetramethylene. Examples of the aromatic heterocyclic group formed by the above R ^g37 and two nitrogen atoms include benzimidazole, benzo [f] benzimidazole, dibenzo [e, g] benzimidazole, benzopyrimidine and the like. .
These groups may have the same substituents as described above.

In the above R ^g38 , ^examples of the alkoxycarbonyl group include groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and butoxycarbonyl. In the present invention, in addition to the above-described charge generating agents, for example, powders of inorganic photoconductive materials such as selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, pyrylium salts, ancesthrone pigments, Conventionally known charge generators such as phenylmethane pigments, sllen pigments, toluidine pigments, pyrazoline pigments, and quinacridone pigments can be used.

The charge generating agents exemplified above are used alone or in combination of two or more so as to have an absorption wavelength in a desired region. Among the above-described charge generating agents, a photoreceptor having sensitivity in a wavelength region of 700 nm or more is required for a digital optical image forming apparatus such as a laser beam printer or a facsimile using a light source such as a semiconductor laser. Therefore, for example, phthalocyanine pigments such as metal-free phthalocyanine represented by the general formula (CG1) and oxotitanyl phthalocyanine represented by the general formula (CG2) are preferably used. The crystal form of the phthalocyanine pigment is not particularly limited, and various types can be used.

On the other hand, an analog optical system image forming apparatus such as an electrostatic copying machine using a white light source such as a halogen lamp requires a photosensitive member having sensitivity in the visible region. Perylene pigments represented by (CG3), bisazo pigments represented by general formula (CG4), and the like are preferably used. << Hole Transport Agent >> In the electrophotographic photoreceptor of the present invention, another conventionally known hole transport agent may be contained in the photosensitive layer together with the stilbene derivative (1) of the present invention which is a hole transport agent. .

As such a hole transporting agent, various compounds having a high hole transporting ability, for example, a compound represented by the following general formula (HT1):
And a compound represented by (HT13).

[0131]

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(Wherein R ^h1 , R ^h2 , R ^h3 , R ^h4 , R ^h5 and R ^h6 are the same or different and each have a halogen atom, an alkyl group which may have a substituent, A and b are the same or different and represent an integer of 0 to 4, and c, d, e and f are the same or different and represent an integer of 0 to 5; An integer, provided that when a, b, c, d, e or f is 2 or more, each of R ^h1 , R ^h2 , R ^h3 , R ^h4 , R ^h5 and R ^h6
May be different. )

[0133]

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(Wherein R ^h7 , R ^h8 , R ^h9 , R ^h10 and R ^h11 are the same or different and each is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, An aryl group which may have a group or a substituent is shown.
g, h, i and j are the same or different and each represents an integer of 0 to 5, and k represents an integer of 0 to 4. Where g, h, i,
When j or k is 2 or more, each of R ^h7 , R ^h8 , R ^h9 , R
^h10 and R ^h11 may be different. )

[0135]

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[0136] (In the ^{formula, R h12, R h13, R} h14 and R ^h15
Represents the same or different and is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. R ^h16
Represents a halogen atom, a cyano group, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. m,
n, o and p are the same or different and represent an integer of 0-5. q shows the integer of 0-6. Where m, n, o, p
Or, when q is 2 or more, each of R ^h12 , R ^h13 , R ^h14 , R
^h15 and R ^h16 may be different. )

[0137]

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( ^Wherein R ^h17 , R ^h18 , R ^h19 and R ^h20
Represents the same or different and is a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. r,
s, t and u are the same or different and each represent an integer of 0-5. However, when r, s, t or u is 2 or more, each R
^{h1 7,} R ^h18, R ^h19 and R ^h20 may be different. )

[0139]

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(In the formula, R ^h21 and R ^h22 are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ^h23 , R ^h24 , R ^h25 and R ^h26 are the same or different and each have a hydrogen atom Represents an atom, an alkyl group or an aryl group.)

[0141]

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(In the formula, R ^h27 , R ^h28 and R ^h29 are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0143]

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( ^Wherein R ^h30 , R ^h31 , R ^h32 and R ^h33
Represents the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. )

[0145]

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(In the formula, R ^h34 , R ^h35 , R ^h36 , R ^h37 and R ^h38 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0147]

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(In the formula, R ^h39 represents a hydrogen atom or an alkyl group, and R ^h40 , R ^h41 and R ^h42 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0149]

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[0150] (wherein, R ^h43, R ^h44 and R ^h45 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0151]

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(In the formula, R ^h46 and R ^h47 are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent. R ^h48 And R ^h49 are the same or different and represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.)

[0153]

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( ^Wherein R ^h50 , R ^h51 , R ^h52 , R ^h53 , R
^h54 and R ^h55 are the same or different and represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. α is 1
And v, w, x, y, z and β are the same or different and represent an integer of 0 to 2. Where v, w,
When x, y, z or β is 2, each of R ^h50 , R ^h51 , R
^h52 , ^Rh53 , ^Rh54 and ^Rh55 may be different. )

[0155]

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( ^Wherein R ^h56 , R ^h57 , R ^h58 and R ^h59
Represents the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and Φ represents the following formula:

[0157]

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The group represented by the formula (Φ-1), (Φ-2) or (Φ-3). In the above-described hole transporting agent, the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the halogen atom include the same groups as described above. Examples of the substituent which may be substituted on the above group include a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms, and a 1 to 1 carbon atom.
And an alkenyl group having 2 to 6 carbon atoms which may have 6 alkoxy groups and aryl groups. The substitution position of the substituent is not particularly limited.

In the present invention, together with or instead of the above-described hole transporting agents (HT1) to (HT13), a conventionally known hole transporting material, ie, 2,5-di (4-methylamino) Oxadiazole compounds such as phenyl) -1,3,4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, 1-phenyl Pyrazoline compounds such as -3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds Compounds, pyrazole compounds,
Nitrogen-containing cyclic compounds such as triazole compounds, condensed polycyclic compounds, and the like can also be used.

In the present invention, only one type of hole transporting agent may be used, or two or more types may be used in combination. Also,
When a hole transporting agent having a film-forming property such as polyvinyl carbazole is used, a binder resin is not necessarily required. << Electron Transport Agent >> Examples of the electron transport agent used in the present invention include various compounds having high electron transport ability, for example, compounds represented by the following general formulas (ET1) to (ET17).

[0161]

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Wherein R ^e1 , R ^e2 , R ^e3 , R ^e4 and R
^e5 are the same or different, a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent,
It represents an aryl group which may have a substituent, an aralkyl group which may have a substituent, a phenoxy group which may have a substituent, or a halogen atom. )

[0163]

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(Where R ^e6 is an alkyl group, R ^e7 is an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, Represents an aralkyl group, a halogen atom or a halogenated alkyl group which may have a group, γ represents an integer of 0 to 5. However, when γ is 2 or more, each ^{Re 7} may be different from each other. )

[0165]

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(In the formula, R ^e8 and R ^e9 are the same or different and each represents an alkyl group. Δ represents an integer of 1 to 4,
Represents an integer of 0 to 4. However, when δ and ε is 2 or more, each R ^e8 and R ^e9 may be different. )

[0167]

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(In the formula, R ^e10 represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogenated alkyl group or a halogen atom. Ζ is 0 to 4, and η is 0 to 5
Indicates an integer. However, when η is 2 or more, each ^{Re 10} may be different. )

[0169]

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(In the formula, R ^e11 represents an alkyl group, and σ represents an integer of 1 to 4. However, when σ is 2 or more, each R
^e11 may be different. )

[0171]

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( ^Wherein R ^e12 and R ^e13 are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyloxycarbonyl group, an alkoxy group,
It represents a hydroxyl group, a nitro group or a cyano group. X represents an oxygen atom, a = N-CN group or a = C (CN) 2 group. )

[0173]

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^Wherein R ^e14 represents a hydrogen atom, a halogen atom, an alkyl group or a phenyl group which may have a substituent, and R ^e15 represents a halogen atom, an alkyl group which may have a substituent or Represents a phenyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group, a cyano group or a nitro group which may have a group, and λ represents an integer of 0 to 3.
However, when λ is 2 or more, each ^{Re e15} may be different from each other. )

[0175]

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(In the formula, θ represents an integer of 1-2.)

[0177]

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( ^Wherein , R ^e16 and R ^e17 are the same or different and each represent a halogen atom, an alkyl group which may have a substituent, a cyano group, a nitro group, or an alkoxycarbonyl group. shows a third integer. However, [nu or ξ is when 2 or more, each R ^e16 and R ^e17 may be different from each other.)

[0179]

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(In the formula, R ^e18 and R ^e19 are the same or different and each represents a phenyl group, a condensed polycyclic group or a heterocyclic group, and these groups may have a substituent.)

[0181]

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( ^Wherein R ^e20 represents an amino group, a dialkylamino group, an alkoxy group, an alkyl group or a phenyl group, and π represents an integer of 1 to 2, provided that when π is 2,
Each R ^{e2 0} may be different from each other. )

[0183]

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( ^Wherein R ^e21 represents a hydrogen atom, an alkyl group,
It represents an aryl group, an alkoxy group or an aralkyl group. )

[0185]

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^Wherein R ^e22 represents a halogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, an alkoxycarbonyl group, an N-alkylcarbamoyl group, a cyano group or a nitro group. Represents an integer of 0 to 3. However, when μ is 2 or more, each ^{Re 22} may be different from each other.)

[0187]

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[0188] (wherein, R ^e23 is a alkyl group or a substituted group may have a substituent indicates also aryl group, R ^e24 represents an alkyl group which may have a substituent, may have an aryl group or a group:. showing a ^-O-R e24a R e24a in the group, represents an aryl group which may have a an optionally substituted alkyl group or a substituted group .)

[0189]

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( ^Where R ^e25 , R ^e26 , R ^e27 , R ^e28 , R
^e29, R ^e30 and R ^e31 represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogen atom or a halogenated alkyl group the same or different. χ and φ
Are the same or different and represent an integer of 0 to 4. )

[0191]

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(In the formula, R ^e32 and R ^e33 are the same or different and each represents an alkyl group, an aryl group, an alkoxy group, a halogen atom or a halogenated alkyl group. Τ and ψ
Are the same or different and represent an integer of 0 to 4. )

[0193]

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^Wherein R ^e34 , R ^e35 , R ^e36 and R ^e37
Represents the same or different and represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group or an amino group. However, ^Re34 , ^Re35 , ^Re36 , R
^At least two of ^e37 are the same groups that are not a hydrogen atom. In the electron transporting agent exemplified above, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group,
Examples of the alkoxycarbonyl group, the heterocyclic group, and the halogen atom include the same groups as described above.

Examples of the alkyl group and the halogen atom in the halogenated alkyl group include the same groups as described above. Examples of the condensed polycyclic group include naphthyl, phenanthryl, anthryl and the like. Examples of the aralkyloxycarbonyl group include those in which the aralkyl moiety is any of the various aralkyl groups described above. Examples of the N-alkylcarbamoyl group include those in which the alkyl moiety is any of the various alkyl groups described above.

Examples of the dialkylamino group include those in which the alkyl moiety is any of the various alkyl groups described above. Even if the two alkyls substituted for amino are the same,
They may be different from each other. Examples of the substituent which may be substituted on each of the above groups include a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. Having 2 to 6 carbon atoms which may have an alkoxy group or an aryl group
And the like. The substitution position of the substituent is not particularly limited.

In the present invention, in addition to the above examples, conventionally known electron transporting substances, for example, benzoquinone compounds, malononitriles, thiopyran compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, Dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromomaleic anhydride and the like can be used.

In the present invention, only one electron transport agent may be used, or two or more electron transport agents may be used in combination. << Binder Resin >> As the binder resin for dispersing the above components, various resins conventionally used in the photosensitive layer can be used. For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-
Maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyvinyl chloride, polypropylene, ionomer, vinyl chloride-vinyl acetate copolymer, Polyester, alkyd resin, polyamide,
Thermoplastic resins such as polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin; silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, and other crosslinkable Thermosetting resin; resins such as photo-curable resins such as epoxy acrylate and urethane-acrylate can be used.

In the photosensitive layer, in addition to the above components, various conventionally known additives such as an antioxidant, a radical scavenger, a singlet quencher, and an ultraviolet absorbing agent may be used as long as the electrophotographic characteristics are not adversely affected. Agents, softeners, plasticizers, surface modifiers, extenders, thickeners, dispersion stabilizers, waxes, acceptors, donors, and the like.
Further, in order to improve the sensitivity of the photosensitive layer, a known sensitizer such as terphenyl, halonaphthoquinones, acenaphthylene and the like may be used in combination with the charge generator.

In the single-layer type photoreceptor, the charge generating agent may be blended in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the binder resin. The stilbene derivative (1) of the present invention may be added in an amount of 20 to 500 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the binder resin. When the electron transporting agent is contained, the ratio of the electron transporting agent is set to the binder resin 1
5 to 100 parts by weight, preferably 10 to 100 parts by weight
It is appropriate that the amount be up to 80 parts by weight. The thickness of the photosensitive layer in the single-layer type photosensitive member is 5 to 100 μm, preferably 10 to 50 μm.

In the laminate type photoreceptor, the charge generating agent and the binder resin constituting the charge generating layer can be used in various ratios, but the charge generating agent is added to 100 parts by weight of the binder resin. It is appropriate to mix at a ratio of １０００1000 parts by weight, preferably 30-500 parts by weight. When the charge generating layer contains a hole transporting agent, the proportion of the hole transporting agent is suitably from 10 to 500 parts by weight, preferably from 50 to 200 parts by weight, based on 100 parts by weight of the binder resin. .

The hole transporting agent and the binder resin constituting the charge transporting layer can be used in various ratios within a range that does not hinder charge transport and a range that does not cause crystallization. The stilbene derivative (1) (hole transporting agent) of the present invention is used in an amount of 10 to 500 parts by weight, preferably 25 to 200 parts by weight, based on 100 parts by weight of the binder resin, so that the charge generated in the above can be easily transported. It is appropriate to mix them in proportions. When the charge transporting layer contains an electron transporting agent, the ratio of the electron transporting agent is 5 to 2 with respect to 100 parts by weight of the binder resin.
The amount is suitably 00 parts by weight, preferably 10 to 100 parts by weight.

The thickness of the photosensitive layer in the laminated photoreceptor is such that the charge generation layer has a thickness of about 0.01 to 5 μm, preferably 0.1 to 5 μm.
The thickness is about 3 μm, and the thickness of the charge transport layer is about 2 to 100 μm, preferably about 5 to 50 μm. In the case of a single-layer type photoreceptor, between the conductive substrate and the photosensitive layer, and in the case of the laminated type photoreceptor, between the conductive substrate and the charge generating layer, between the conductive substrate and the charge transport layer, or A barrier layer may be formed between the generation layer and the charge transport layer as long as the characteristics of the photoreceptor are not impaired. Further, a protective layer may be formed on the surface of the photoconductor.

As the conductive substrate on which the photosensitive layer is formed, various conductive materials can be used.
For example, iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, brass and other simple metals, and plastic materials on which the above metals are deposited or laminated, Glasses coated with aluminum iodide, tin oxide, indium oxide, and the like can be given.

The conductive substrate may be in the form of a sheet, a drum, or the like, depending on the structure of the image forming apparatus to be used. The substrate itself has conductivity, or the surface of the substrate is conductive. What is necessary is just to have the property. The conductive substrate preferably has a sufficient mechanical strength when used. When the photosensitive layer is formed by a coating method, the above-described charge generating agent, charge transporting agent, binder resin, and the like, together with a suitable solvent, are mixed with a known method, for example, a roll mill, a ball mill, an attritor, a paint shaker, What is necessary is just to disperse and mix using a sonic disperser or the like to prepare a dispersion, apply it by a known means, and dry it.

As the solvent for preparing the dispersion, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol; and aliphatic hydrocarbons such as n-hexane, octane and cyclohexane. Hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether Ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate; dimethyl formaldehyde, dimethyl formamide, dimethyl sulfo Sid and the like. These solvents are used alone or in combination of two or more.

Further, in order to improve the dispersibility of the charge transporting agent and the charge generating agent and the smoothness of the surface of the photosensitive layer, a surfactant is used.
A leveling agent or the like may be used.

[0208]

The present invention will be further described based on Reference Examples, Synthesis Examples, Examples and Comparative Examples. << Synthesis of Stilbene Derivative >> Reference Example 1 [Synthesis of α, α′-dichloromethylstilbene (91 ′)] The title compound was synthesized according to the following reaction formula.

[0209]

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1) A flask equipped with Dean Stark and a reflux tube was charged with parachloromethylbenzoic acid (97 ') 1.
7 g, 11.1 g (1.5-fold mol) of n-butanol and 300 ml of toluene as a solvent were added, and the mixture was refluxed for 8 hours.
After completion of the reaction, the product was recrystallized from methanol to obtain 18 g of butyl chloromethylbenzoate (98 ') (yield: 8).
0%).

2) The above compound (98) is reacted with a phosphite triester to give a monophosphate ester derivative (9
9 ′) was obtained. This compound (99 ′) was reacted with methyl p-aldehyde benzoate to obtain stilbene dicarboxylic acid ester (100 ′). That is, 10 g of the compound (98) and 8.3 g (1.2-fold mol) of the phosphite triester were placed in a flask equipped with a reflux tube and refluxed for 3 hours. After the completion of the reaction, the product was recrystallized from hexane to obtain 13.3 g of a monolinsan ester (99 ′) (yield: 92%). 10 g of monophosphate and 0.73 g (equimolar) of degassed and dried sodium hydride were added to THF 200
The mixture was added to the mixture and cooled on ice. To this, 7.28 g (1.0 g of methyl p-aldehyde benzoate) dissolved in 50 ml of THF was added.
(1 mol) was added dropwise and reacted at room temperature for about 3 hours. After the reaction, the reaction solution was added to 400 ml of a dilute hydrochloric acid aqueous solution of about 2%, and the precipitated crystals were filtered and washed with water. After drying the crystals, silica gel column chromatography (developing solvent: chloroform)
/ Hexane mixed solvent) to obtain a compound (100 ′). 14.27 g (yield 87%) 3) In a flask equipped with a reflux tube under an argon atmosphere,
Tetrohydrofuran (TH) containing 1.12 g (2 times mol) of lithium aluminum hydride (reducing agent, LAH)
F) A solution was added, and 50 ml of a THF solution containing 10 g of stilbene dicarboxylic acid ester (100 ′) was added dropwise thereto. Next, after stirring at room temperature for about 6 hours, the reaction solution was poured into an ice bath, and the product was extracted with ethyl acetate and washed thoroughly with water. Ethyl acetate was distilled off to obtain 6.53 g of stilbenedihydroxymethyl (101 ′) (yield: 92%).

4) A flask equipped with a reflux tube was charged with 5 g of stilbenebishydroxymethyl (96 '), 10 g of thionyl chloride serving also as a solvent and a reagent, and a catalytic amount of pyridine as a phase transfer catalyst, and refluxed for 8 hours. did. After completion of the reaction, the solvent was distilled off, and the product was recrystallized from methanol to obtain 4.61 g of the title compound α, α′-dichloromethylstilbene (91 ′) (80% yield).

Reference Example 2 [Synthesis of bisphosphate ester (3)] 6.47 g (2.4 times mol) of phosphite triester was added to 4.5 g of α, α'-dichloromethylstilbene (91 '). Plus 3
After refluxing for an hour, the solvent was distilled off, and the residue was recrystallized from hexane to give the compound of the following formula bisphosphate (3p) 6.7.
9 g was obtained (87% yield).

[0214]

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In the same manner as above, the bisphosphate ester derivative represented by the above formula (3m) using metachloromethylbenzoic acid as a starting compound, and the bisphosphoric acid ester derivative represented by the above formula (3m) using orthochloromethylbenzoic acid as a starting compound. The obtained bisphosphate ester derivatives were obtained. Reference Example 3 [Synthesis of 2,6-dimethyltriphenylamine] 2,6
-15 g (124 mmol) of dimethylaniline, 50 g (245 mmol) of iodobenzene, 17 g (123 mmol) of anhydrous potassium carbonate and 1 g (16 mmol) of powdered copper are added in 150 ml of nitrobenzene,
The reaction was performed under reflux for about 24 hours. After the reaction, the inorganic salt was removed, and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform / hexane) to obtain 28.8 g of the title compound (yield: 85%).

Reference Example 4 [Synthesis of 2-methyl-6-ethyltriphenylamine]
The reaction was carried out in the same manner as in Reference Example 1 except that the same molar amount of 6-ethyl-0-toluidine was used instead of 2,6-dimethylaniline to obtain 31.0 g of the title compound (yield: 85%).

Reference Example 5 [Synthesis of 2,6-diethyltriphenylamine] 2,6
The reaction was carried out in the same manner as in Reference Example 1 except that the same molar amount of 2,6-diethylaniline was used instead of -dimethylaniline,
31.0 g of the title compound were obtained (83% yield).

Reference Example 6 [Synthesis of 2-isopropyl-6-methyltriphenylamine] Reference Example 1 was repeated except that the same molar amount of 6-isopropyl-o-toluidine was used in place of 2,6-dimethylaniline.
The reaction was carried out in the same manner as described above to obtain 3.4 g of the title compound (yield 84%).

Reference Example 7 [Synthesis of 2-isopropyl-6-ethyltriphenylamine] Instead of 2,6-dimethylaniline, 2-ethyl-
The reaction was carried out in the same manner as in Reference Example 1 except that the same molar amount of 6-isopropylaniline was used, to obtain 31.3 g of the title compound (yield: 80%).

Reference Example 8 [Synthesis of 2-t-butyl-6-methyltriphenylamine] Reference Example 8 was repeated except that the same molar amount of 6,5-butyl-6-toluidine was used in place of 2,6-dimethylaniline. The reaction was carried out in the same manner as in Example 1 to obtain 30.1 g of the title compound (yield: 7).
7%).

Reference Example 9 [Synthesis of 2-s-butyl-6-ethyltriphenylamine] Instead of 2,6-dimethylaniline, 2-ethyl-6 was used.
Reference Example 1 except that the same molar amount of -5-butylaniline was used.
The reaction was carried out in the same manner as in the above to give 31.3 g of the title compound (yield: 80%). Reference Example 10 [Synthesis of 2,6-dimethyl-4'-formyltriphenylamine] 2,6-dimethyltriphenylamine 28 g
(102 mmol) in dimethylformamide (DMF)
Dissolve in 300 ml and add 16 g of phosphoric acid oxychloride
(104 mmol) and reacted at 40 ° C. for 1 hour. After the reaction, the reaction mixture was added to 300 ml of water and extracted with ethyl acetate. Next, the organic layer was washed with water and dried to remove the solvent, and the residue was purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform / hexane) to obtain 26.8 g (yield 87%) of the title compound. .

Reference Example 11 [Synthesis of 2-methyl-6-ethyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2-methyl-6-ethyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Reference Example 10 except for using
28.2 g of the title compound were obtained (yield 87%).

Reference Example 12 [Synthesis of 2,6-diethyl-4'-formyltriphenylamine] Except that 2,6-diethyltriphenylamine was used in the same molar amount as 2,6-dimethyltriphenylamine. The reaction was carried out in the same manner as in Reference Example 11 to give the title compound 2
7.1 g were obtained (80% yield).

Reference Example 13 [Synthesis of 2-isopropyl-6-methyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2-isopropyl-6-methyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Reference Example 11 except for using the compound, to obtain 28.6 g of the title compound (yield: 85).
%).

Reference Example 14 [Synthesis of 2-isopropyl-6-ethyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2-isopropyl-6-ethyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Reference Example 11 except for using the compound, to obtain 28 g of the title compound (yield: 80%).

Reference Example 15 [Synthesis of 2-t-butyl-6-methyl-4'-formyltriphenylamine] 2-t-butyl-6-methyltriphenylamine was substituted for 2,6-dimethyltriphenylamine. The reaction was carried out in the same manner as in Reference Example 11 except for using the same molar amount, to obtain 27.3 g of the title compound (78% yield).

Reference Example 16 [Synthesis of 2-s-butyl-6-ethyl-4'-formyltriphenylamine] Instead of 2,6-dimethyltriphenylamine, 2-s-butyl-6-ethyltriphenylamine was replaced with 2-s-butyl-6-ethyltriphenylamine. The reaction was carried out in the same manner as in Reference Example 11, except that the same molar amount was used, to obtain 28.8 g of the title compound (79% yield).

Synthesis Example 1 [Stilbene derivative (11-1)
Synthesis of bisphosphonate ester represented by the above formula (3p) 7.5 g (1
5.6 mmol) and degassed and dried sodium hydride 0.
75 g (31.2 mmol) with tetrahydrofuran 2
The mixture was added to 00 ml and cooled on ice. To this, 9.5 g (31.5 mmol) of 2,6-dimethyl-4'-formyltriphenylamine dissolved in tetrahydrofuran
Was added dropwise and reacted at room temperature for about 3 hours. After the reaction, about 2%
Was added to 400 ml of a diluted aqueous hydrochloric acid solution, and the precipitated crystals were filtered and washed with water. After the crystals were dried, they were purified by silica gel column chromatography (developing solvent: mixed solvent of chloroform / hexane) to obtain 8.1 g of a stilbene derivative represented by Compound No. 11-1 in Table 1 (yield 67%). .

Synthesis Example 2 [Stilbene derivative (11-2)
Synthesis of Synthesis Example 1 except that 2-ethyl-6-methyl-4'-formyltriphenylamine was used in the same molar amount in place of 2,6-dimethyl-4'-formyltriphenylamine. And the reaction was carried out.
8.7 g of the stilbene derivative represented by 1-2 was obtained (70% yield).

Melting point: 141 to 143 ° C. FIG. 1 shows an infrared absorption spectrum of the stilbene derivative (11-2). Synthesis Example 3 [Synthesis of stilbene derivative (11-3)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2,6-diethyl-4'-formyltriphenylamine was used in the same molar amount. Otherwise, the reaction was carried out in the same manner as in Synthesis Example 1.
Was obtained (yield 70).
%).

Synthesis Example 4 [Synthesis of stilbene derivative (11-4)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 2-isopropyl, 6-methyl-4'-formyltriphenylamine was used. The reaction was carried out in the same manner as in Synthesis Example 1 except that the same molar amount was used, to obtain 8.8 g of a stilbene derivative represented by Compound No. 11-4 in Table 1 (yield: 68%).

Synthesis Example 5 [Synthesis of stilbene derivative (11-5)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2-isopropyl and 6-ethyl-4'-formyltriphenylamine were used. The reaction was carried out in the same manner as in Synthesis Example 1 except that the same molar amount was used, to obtain 8.7 g of the stilbene derivative represented by Compound No. 11-5 in Table 1 (yield: 65%).

Synthesis Example 6 [Synthesis of stilbene derivative (11-6)] In place of 2,6-dimethyl-4'-formyltriphenylamine, t-butyl and 6-methyl-4'-formyltriphenylamine were used. The reaction was carried out in the same manner as in Synthesis Example 1 except that the same molar amount was used.
8.4 g of the stilbene derivative represented by 1-6 was obtained (63% yield).

Synthesis Example 7 [Synthesis of stilbene derivative (11-7)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 2-s-butyl, 6-ethyl-4'-formyltriphenyl The reaction was carried out in the same manner as in Synthesis Example 1 except that the amine was used in the same molar amount, to obtain 9.0 g of the stilbene derivative represented by the compound number 11-7 in Table 1 (yield: 65%).

Synthesis Example 8 [Synthesis of Stilbene Derivative (12-1)] In Synthesis Example 1, the bisphosphate ester represented by the above formula (3m) was replaced with the bisphosphate ester represented by the above formula (3p). The reaction was carried out in the same manner as in Synthesis Example 1 except that the same molar amount was used, to obtain 7.4 g of a stilbene derivative represented by Compound No. 12-3 in Table 2 (yield: 61%).

Synthesis Examples 9 to 21 The following compounds were synthesized according to the methods described above. (Synthesis Example 9) Stilbene derivative (12-2) Yield
1 g (65% yield) (Synthesis Example 10) Stilbene derivative (12-3) Yield
2 g (63% yield) (Synthesis Example 11) Stilbene derivative (12-4) Yield
3 g (64% yield) (Synthesis Example 12) Stilbene derivative (12-5) Yield
0 g (60% yield) (Synthesis Example 13) Stilbene derivative (12-6) Yield 7.
8 g (58% yield) (Synthesis Example 14) Stilbene derivative (12-7) Yield
3 g (60% yield) (Synthesis Example 15) Stilbene derivative (13-1) Yield
6 g (yield 71%) (Synthesis Example 16) Stilbene derivative (13-2) Yield
8 g (yield 70%) (Synthesis Example 17) Stilbene derivative (13-3) Yield 9.
1 g (yield 70%) (Synthesis Example 18) Stilbene derivative (13-4) Yield
7 g (67% yield) (Synthesis Example 19) Stilbene derivative (13-5) Yield
4 g (63% yield) (Synthesis Example 20) Stilbene derivative (13-6) Yield
4 g (63% yield) (Synthesis Example 21) Stilbene derivative (13-7) Yield 9.
7 g (70% yield) << Production of Electrophotographic Photoreceptor >> (Single-Layer Photoreceptor for Digital Light Source) Example 1 X-type metal-free phthalocyanine (CG1-1) was used as a charge generating agent. The hole transporting agents include the compound numbers (11-
The stilbene derivative represented by 1) was used.

5 parts by weight of the above-mentioned charge generating agent and 10 parts of the hole transporting agent
0 parts by weight and 100 parts by weight of a binder resin (polycarbonate) were mixed and dispersed in a ball mill for 50 hours together with 800 parts by weight of a solvent (tetrahydrofuran) to prepare a coating solution for a single-layer type photosensitive layer. Next, this coating solution is applied onto a conductive substrate (aluminum tube) by dip coating, and dried with hot air at 100 ° C. for 30 minutes to form a single layer for a digital light source having a single-layer photosensitive layer having a thickness of 25 μm. A layer type photoreceptor was manufactured. Example 2 As a hole transport agent, the compound number (11-2) shown in Table 1 above
Example 1 except that the stilbene derivative represented by
A single-layer photoreceptor for a digital light source was manufactured in the same manner as described above.

Example 3 Compound No. (11-3) shown in Table 1 above as a hole transporting agent
Example 1 except that the stilbene derivative represented by
A single-layer photoreceptor for a digital light source was manufactured in the same manner as described above. Example 4 In a coating solution for a single-layer type photosensitive layer, an electron transporting agent represented by the following formula (ET17-1):

[0239]

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A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Example 1, except that 30 parts by weight of the diphenoquinone derivative represented by the formula (1) was blended. Example 5 As a hole transporting agent, the compound number (11-2) shown in Table 1 above
Example 4 except that the stilbene derivative represented by
A single-layer photoreceptor for a digital light source was manufactured in the same manner as described above.

Example 6 Compound No. (11-3) shown in Table 1 was used as a hole transporting agent.
Example 1 except that the stilbene derivative represented by
A single-layer photoreceptor for a digital light source was manufactured in the same manner as described above. Examples 7 to 9 As an electron transporting agent, a compound represented by the formula (ET14-1):

[0242]

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A single-layer photosensitive member for a digital light source was manufactured in the same manner as in Examples 4 to 6, except that the naphthoquinone derivative represented by Examples 10 to 12 As an electron transporting agent, a compound represented by the formula (ET14-2):

[0244]

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A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Examples 4 to 6, except that the naphthoquinone derivative represented by the following formula was used. Examples 13 and 14 As the hole transporting agent, the compound number (12-2) shown in Table 2 above
In the same manner as in Example 1, except that the stilbene derivative represented by the following formula or the stilbene derivative represented by the compound number (13-2) in Table 3 was used, a single-layer photosensitive member for a digital light source was manufactured. .

Examples 15 and 16 Compounds (12-2) in Table 2 were used as hole transporting agents.
In the same manner as in Example 4, except that the stilbene derivative represented by the formula (1) or the stilbene derivative represented by the compound number (13-2) in Table 3 was used, single-layer photosensitive members for digital light sources were manufactured. .

Examples 17 and 18 Compounds (12-2) shown in Table 2 above were used as hole transporting agents.
In the same manner as in Example 7, except that the stilbene derivative represented by the formula (1) or the stilbene derivative represented by the compound number (13-2) in Table 3 was used, single-layer photosensitive members for digital light sources were manufactured. .

Examples 19 and 20 As the hole transporting agent, the compound number (12-2) shown in Table 2 was used.
In the same manner as in Example 10, except that the stilbene derivative represented by the following formula (1) or the stilbene derivative represented by the compound number (13-2) in Table 3 was used, single-layer photoconductors for digital light sources were manufactured. .

Comparative Example 1 As a hole transporting agent, a compound represented by the formula (6-1):

[0250]

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A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Example 1 except that the stilbene derivative represented by the following formula was used. Comparative Example 2 Formula (6-2):

[0252]

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A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 1 except that the stilbene derivative represented by the following formula was used. Comparative Example 3 As a hole transporting agent, a compound represented by the formula (6-3):

[0254]

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A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Example 1 except that the stilbene derivative represented by the following formula was used. Comparative Example 4 As a hole transporting agent, a compound represented by the formula (6-4):

[0256]

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A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Example 1 except that the stilbene derivative represented by the following formula was used. Comparative Example 5 As a hole transporting agent, a compound represented by the formula (6-5):

[0258]

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A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 1 except that the stilbene derivative represented by the following formula was used. Examples 1 to 20 and Comparative Examples 1 to 5
The following electrical property test (I) was performed on the photoreceptors obtained in the above, and the electrical properties of each photoreceptor were evaluated. Electric property test (I) Applying an applied voltage to the surface of each photoreceptor using a drum sensitivity tester manufactured by GENTEC, and applying +70 to the surface
After charging to 0 ± 20 V, the surface potential Vo (V) was measured. Next, a wavelength 78 extracted from white light of a halogen lamp as an exposure light source using a bandpass filter.
0 nm monochromatic light (half-width 20 nm, light intensity 8 μJ / cm
2) was irradiated onto the surface of the photoreceptor (irradiation time: 1.5 seconds), the time required for the surface potential Vo to become 1/2 was measured, and the half-life exposure amount E1 / 2 (μJ / cm 2) Was calculated. In addition, the surface potential at the time when 0.5 seconds had elapsed from the start of exposure was measured as the residual potential Vr (V).

Table 4 shows the types of the charge generating agent, the hole transporting agent and the electron transporting agent used in each of the above Examples and Comparative Examples, and the test results of the electrical characteristics. In the following tables, the types of the charge generating agent, the hole transporting agent and the electron transporting agent are indicated by the respective formula numbers or the numbers assigned to the compounds.

[0261]

[Table 4]

Examples 21 to 23 As the charge generating agent, α-oxotitanyl phthalocyanine (C
A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Examples 1 to 3, except that G2-1) was used. Examples 24 to 26 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 4 to 6.

Examples 27 to 29 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 7 to 9. Examples 30 to 32 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoconductors for digital light sources were manufactured in the same manner as in Examples 10 to 12.

Examples 33 and 34 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 13 and 14. Examples 35 and 36 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Examples 15 and 16, except that G2-1) was used.

Examples 37 and 38 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoconductors for digital light sources were manufactured in the same manner as in Examples 17 and 18. Examples 39 and 40 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 19 and 20, respectively.

Comparative Examples 6 to 10 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Comparative Examples 1 to 5. The electrical characteristics test (I) was performed on the photoconductors obtained in Examples 21 to 40 and Comparative Examples 6 to 10 to evaluate the electrical characteristics of each photoconductor. Table 5 shows the types of the charge generating agent, the hole transporting agent, and the electron transporting agent used in each of the examples and the comparative examples, and the test results of the electrical characteristics.

[0267]

[Table 5]

Examples 21 to 23 As a charge generating agent, α-type oxotitanyl phthalocyanine (C
A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Examples 1 to 3, except that G2-1) was used. Examples 24 to 26 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 4 to 6.

Examples 27 to 29 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 7 to 9. Examples 30 to 32 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoconductors for digital light sources were manufactured in the same manner as in Examples 10 to 12.

Examples 33 and 34 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 13 and 14. Examples 35 and 36 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Examples 15 and 16, except that G2-1) was used.

Examples 37 and 38 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoconductors for digital light sources were manufactured in the same manner as in Examples 17 and 18. Examples 39 and 40 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 19 and 20, respectively.

Comparative Examples 6 to 10 α-oxotitanyl phthalocyanine (C
Except for using G2-1), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Comparative Examples 1 to 5. Examples 41 to 60 Y-type oxotitanyl phthalocyanine (C
Except for using G2-2), single-layer photoreceptors for digital light sources were manufactured in the same manner as in Examples 21 to 40.

Comparative Examples 11 to 15 Y-type oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was produced in the same manner as in Comparative Examples 1 to 5, except that G2-2) was used. The electrical characteristics test (I) was performed on the photoconductors obtained in Examples 41 to 60 and Comparative Examples 11 to 15 to evaluate the electrical characteristics of each photoconductor. Table 6 shows the types of the charge generating agent, the hole transporting agent, and the electron transporting agent used in each of the examples and the comparative examples, and the test results of the electrical characteristics.

[0274]

[Table 6]

(Laminated Photoreceptor for Digital Light Source) Example 61 X-Type Metal-Free Phthalocyanine (CG1-1) as Charge Generator
2.5 parts by weight and binder resin (polyvinyl butyral)
One part by weight was mixed and dispersed in a ball mill together with 15 parts by weight of a solvent (tetrahydrofuran) to prepare a coating liquid for a charge generation layer. Next, this coating solution was applied on a conductive substrate (aluminum pipe) by dip coating, and
The resultant was dried with hot air at 0 ° C. for 30 minutes to form a charge generation layer having a thickness of 0.5 μm.

Next, 1 part by weight of a stilbene derivative (11-1) as a hole transporting agent and 1 part by weight of a binder resin (polycarbonate) were mixed and dispersed in a ball mill together with 10 parts by weight of a solvent (tetrahydrofuran) to obtain a charge. A coating solution for the transport layer was prepared. Next, this coating solution was applied on the charge generation layer by dip coating, and dried with hot air at 110 ° C. for 30 minutes to form a charge generation layer having a thickness of 20 μm.
A laminated photoreceptor for a digital light source was manufactured.

Example 62 A laminated photoreceptor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (11-2) was used as the hole transporting agent. Example 63 A laminated photoconductor for a digital light source was produced in the same manner as in Example 61 except that the stilbene derivative (11-3) was used as the hole transporting agent.

Examples 64 to 66 α-oxotitanyl phthalocyanine (C
A laminated photoreceptor for a digital light source was manufactured in the same manner as in Examples 61 to 63 except that G2-1) was used. Examples 67 to 69 Y-type oxotitanyl phthalocyanine (C
Except for using G2-2), multilayer photoreceptors for digital light sources were manufactured in the same manner as in Examples 61 to 63.

Examples 70 and 71 A laminated photoreceptor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent. did. Examples 72 and 73 Except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent, a laminated photoconductor for a digital light source was manufactured in the same manner as in Example 64.

Examples 74 and 75 Laminated photoreceptors for digital light sources were produced in the same manner as in Example 67 except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent. did. Comparative Examples 16 to 18 Except that the stilbene derivative (6-1) was used as a hole transporting agent, a laminated photoconductor for a digital light source was manufactured in the same manner as in Examples 61, 64 and 67.

Comparative Examples 19 to 20 Except that the stilbene derivative (6-4) was used as a hole transporting agent, a laminated photoreceptor for a digital light source was produced in the same manner as in Examples 61, 64 and 67. Comparative Examples 21 to 24 Except that the stilbene derivative (6-5) was used as the hole transporting agent, a laminated photoconductor for a digital light source was manufactured in the same manner as in Examples 61, 64 and 67.

Examples 61 to 75 and Comparative Examples 21 to 75
The following electrical characteristics test (II) of the photoreceptor obtained in 24
And evaluated the electrical characteristics of each photoconductor. Electrical characteristics test (II) Except that the surface of the photoreceptor was charged to -700 ± 20V,
Surface potential Vo in the same manner as in the electrical characteristic test (I).
(V), residual potential Vr (V) and half-exposure amount E1 /
2 (μJ / cm 2) was determined.

Table 7 shows the types of the charge generating agent and the hole transporting agent used in each of the above Examples and Comparative Examples, and the test results of the electrical characteristics.

[0284]

[Table 7]

(Single-layer type photoreceptor for analog light source) Examples 76 to 95 The following formula (CG3-1) was used as a charge generating agent:

[0286]

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[0287] Except for using the perylene pigment represented by
In the same manner as in Examples 1 to 20, single-layer photoconductors for analog light sources were manufactured. Comparative Examples 25 to 29 In the same manner as in Comparative Examples 1 to 5, except that a perylene pigment (CG3-1) was used as the charge generating agent, single-layer photoconductors for analog light sources were manufactured.

The above Examples 76 to 95 and Comparative Examples 25 to
The following electrical property test (II
I) was performed to evaluate the electrical characteristics of each photoconductor. Electric property test (III) The surface potential Vo (V) and residual potential Vr (V) were obtained in the same manner as in the electric property test (I), except that white light (light intensity of 8 lux) of a halogen lamp was used as an exposure light source. ) And half-exposure amount E1 / 2 (lux · sec).

Table 8 shows the types of the charge generating agent, the hole transporting agent and the electron transporting agent used in each of the above Examples and Comparative Examples, and the test results of the electrical characteristics.

[0290]

[Table 8]

Examples 96 to 115 As a charge generator, a compound of the formula (CG4-1):

[0292]

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Except that the bisazo pigment represented by the following formula was used,
In the same manner as in Examples 76 to 95, single-layer photoconductors for analog light sources were manufactured. Comparative Examples 30 to 34 Single-layer photoconductors for analog light sources were manufactured in the same manner as in Comparative Examples 25 to 29 except that bisazo pigment (CG4-1) was used as the charge generator.

Examples 96 to 115 and Comparative Example 25
To 29, the electrical characteristics test (II
I) was performed to evaluate the electrical characteristics of each photoconductor. Table 9 shows the types of the charge generating agent, the hole transporting agent, and the electron transporting agent used in each of the examples and the comparative examples, and the test results of the electrical characteristics.

[0295]

[Table 9]

Examples 116 to 135 As a charge generator, a compound of the formula (CG4-2):

[0297]

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Except that the bisazo pigment represented by the following formula was used,
In the same manner as in Examples 76 to 95, a single-layer type photosensitive member for an analog light source was manufactured. Comparative Examples 35 to 39 Single-layer photoreceptors for analog light sources were manufactured in the same manner as in Comparative Examples 25 to 29 except that bisazo pigment (CG4-2) was used as the charge generator.

Examples 116 to 135 and Comparative Example 2
With respect to the photoconductors obtained in Nos. 5 to 29, the above-described electrical property test (I
II) was performed to evaluate the electrical characteristics of each photoconductor. Table 10 shows the types of the charge generating agent, the hole transporting agent, and the electron transporting agent used in each of the examples and the comparative examples, and the test results of the electrical characteristics.

[0300]

[Table 10]

Examples 136 to 155 The following formula (CG4-3) was used as a charge generating agent.

[0302]

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Except that the bisazo pigment represented by
In the same manner as in Examples 76 to 95, a single-layer type photosensitive member for an analog light source was manufactured. Comparative Examples 40 to 44 Single-layer photoconductors for analog light sources were manufactured in the same manner as in Comparative Examples 25 to 29 except that bisazo pigment (CG4-3) was used as the charge generator.

Examples 136 to 155 and Comparative Example 2
With respect to the photoconductors obtained in Nos. 5 to 29, the above-described electrical property test (I
II) was performed to evaluate the electrical characteristics of each photoconductor. Table 11 shows the types of the charge generating agent, the hole transporting agent and the electron transporting agent used in each of the examples and the comparative examples, and the test results of the electrical characteristics.

[0305]

[Table 11]

(Laminated Photoconductor for Analog Light Source) Examples 156 to 158 The laminated photoconductor for an analog light source was prepared in the same manner as in Examples 61 to 63 except that perylene pigment (CG3-1) was used as a charge generating agent. Body manufactured. Examples 159 to 161 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 63 except that a bisazo pigment (CG4-1) was used as a charge generator.

Examples 162 to 164 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 63 except that a bisazo pigment (CG4-2) was used as a charge generator. Examples 165 to 167 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 63 except that a bisazo pigment (CG4-3) was used as a charge generator.

Examples 168 and 169 A laminated photoreceptor for an analog light source was produced in the same manner as in Example 156 except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent. did. Examples 170 and 171 Except that the stilbene derivative (12-2) or (13-2) was used as a hole transporting agent, a laminated photoconductor for an analog light source was manufactured in the same manner as in Example 162.

Examples 172 and 173 Except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent, a laminated photoreceptor for an analog light source was manufactured in the same manner as in Example 156. did. Examples 174 and 175 Laminated photoconductors for analog light sources were manufactured in the same manner as in Example 165 except that the stilbene derivative (12-2) or (13-2) was used as the hole transporting agent.

Comparative Examples 45 to 48 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 156, 159, 162 and 165, except that the stilbene derivative (6-1) was used as the hole transporting agent. . Comparative Examples 49 to 52 Laminated photoconductors for analog light sources were manufactured in the same manner as in Examples 156, 159, 162 and 165, except that the stilbene derivative (6-4) was used as the hole transporting agent.

Examples 156 to 175 and Comparative Example 4
The following electrical property tests were performed on the photoreceptors obtained in 5-52.
(IV) was performed to evaluate the electrical characteristics of each photoconductor. Electrical characteristics test (IV) Except that the surface of the photoreceptor was charged to -700 ± 20V,
In the same manner as in the electrical characteristic test (III), the surface potential Vo
(V), residual potential Vr (V) and half-exposure amount E1 /
2 (lux · sec) was determined.

[0312] Table 12 shows the types of the charge generating agent and the hole transporting agent used in each of the above Examples and Comparative Examples, and the test results of the electrical characteristics.

[0313]

[Table 12]

As apparent from Tables 4 to 12, Example 1
The electrophotographic photoreceptors No. to No. 175 have a smaller absolute value of the residual potential Vr than the comparative examples corresponding to the respective examples. Also, the half-life exposure amount E1 / 2 is equal to or less than the value in the corresponding comparative example. This indicates that the electrophotographic photosensitive members of Examples 1 to 175 have excellent sensitivity.

Test Example (Evaluation on Compatibility with Binder Resin) For the stilbene derivatives of the above compound numbers 11-1 to 3, 12-2 and 13-2, the compatibility with the binder resin was determined by the following method. Was evaluated. (Preparation of Sample) Compound Nos. 11-1 to 11-2, 13-2 and 13 were added to a mixture of 100 parts by weight of a binder resin (polycarbonate) and 800 parts by weight of a solvent (tetrahydrofuran).
The stilbene derivative of No. -2 was blended in an amount of 1 to 100 parts by weight, and the maximum amount (parts by weight) of the stilbene derivative capable of obtaining a uniform coating solution was determined. The coating solution was prepared by mixing and dispersing the above components for 50 hours using a roll mill.

Next, the maximum addition amount (parts by weight) of each of the above stilbene derivatives was substituted into the following equation to determine the blending ratio (% by weight) of the stilbene derivative to the binder resin, and the solubility in the binder resin was evaluated. did. The higher the blending ratio, the better the solubility in the binder resin.

[0317]

(Equation 1)

As control compounds, the above (6-1) to
Using the stilbene derivative of (6-5), the solubility in the binder resin was evaluated in the same manner as described above. Table 1 shows these results.
3 is shown.

[0319]

[Table 13]

As is clear from Table 2, the stilbene derivatives of the present invention are the same as those of the conventional stilbene derivatives (6-1) to (6).
Compared with -5), the solubility in the binder resin is excellent.

[0321]

Industrial Applicability The stilbene derivative (1) of the present invention has high compatibility with a binder resin and has high charge transport ability (hole transport ability). Further, the electrophotographic photoreceptor of the present invention has high sensitivity because the stilbene derivative (1) is used as a hole transporting agent. Therefore, the electrophotographic photoreceptor of the present invention has a specific function and effect that contributes to speeding up and improving performance of various image forming apparatuses such as an electrostatic copying machine and a laser beam printer.

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of a stilbene derivative (11-2).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03G 5/06 313 G03G 5/06 313 F term (Reference) 2H068 AA20 AA21 AA31 BA13 4H006 AA01 AA02 AB76 AC25 AC45 AC52 BJ50 BP30 BU46 4H056 DA03 DB10 FA05

Claims (6)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ and R ³ are the same or different and each may have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or alkoxy group which may have a substituent group, R ² and R ⁴ are the same or different and which may have a substituent group or an optionally substituted alkoxy group.) A stilbene derivative represented by the formula: 2. The stilbene derivative according to claim 1, wherein R ¹ and R ³ in the general formula (1) are the same group, and R ² and R ⁴ are the same group. 3. A compound of the general formula (2) (In the formula, R ¹ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. even when the alkoxy group, a formylated triphenylamine derivative represented by R ² is an alkoxy group which may have an optionally substituted alkyl group or a substituent.), general Formula (3) 3. The method for producing a stilbene derivative according to claim 2, wherein the reaction is carried out with a bisphosphate ester derivative represented by the formula: 4. A method according to claim 1, wherein said formylated triphenylamine derivative (2) has the general formula (4): (In the formula, R ¹ has an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a substituent. R ² represents an alkyl group which may have a substituent or an alkoxy group which may have a substituent.) , General formula (5): 4. The process according to claim 3, wherein a triphenylamine derivative represented by the formula (wherein R ¹ and R ² have the same meanings as described above) is obtained, and this compound is obtained by formylation by the Vilsmeier method. Method. 5. An electrophotographic photosensitive member having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer contains a stilbene derivative represented by the general formula (1) according to claim 1 or 2. An electrophotographic photosensitive member characterized by the following. 6. A single-layered photosensitive layer containing a stilbene derivative represented by the general formula (1) according to claim 1 or 2 together with a charge generating agent and an electron transporting agent. Item 6. The electrophotographic photosensitive member according to Item 5.