JP2000239236A - Stilbene derivative, its production and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new compound excellent in compatibility with a binder resin, having a high charge mobility and suitable as a charge transporting agent for an electrophotographic photoreceptor. SOLUTION: A compound represented by formula X [R1 and R3 are each a (substituted)alkyl, a (substituted)aryl or the like; R2 and R4 are each H, a (substituted)alkyl or a (substituted)alkoxy, with the proviso that R2 and R4 are each H when the substituted positions of the R2 and R4 are the 4(para)- positions]. The above compound is produced by reacting (A) a formylated triphenylamine derivative represented by formula II used in a molar amount of 1.8-2.5 times based on (B) a bisphosphoric ester derivative represented by formula III with the component B in the presence of a base such as sodium methoxide in a solvent such as diethyl ether at a reactional temperature within the range of -10 to +25 deg.C for about 3-12 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stilbene derivative having an excellent charge transporting ability, a method for producing the same, and the stilbene derivative containing the stilbene derivative and used in an image forming apparatus such as an electrostatic copying machine, a facsimile, a laser beam printer, etc. To an electrophotographic photoreceptor.

[0002]

2. Description of the Related Art In the above-mentioned image forming apparatus, various organic photosensitive members having sensitivity in a wavelength region of a light source used in the image forming 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. Due to its advantages, it has been widely used in recent years.

[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.

[0004]

The stilbene derivatives are disclosed in JP-A-50-31773 and JP-A-7-244389 as charge transporting agents used in the above-mentioned organic photoreceptors.

[0005] 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, the stilbene derivative itself has a high charge mobility, but when this is used for a photoreceptor as a charge transport agent, its characteristics cannot be sufficiently exhibited,
The residual potential of the photoconductor becomes high, and the light sensitivity becomes insufficient.

Accordingly, an object of the present invention is to solve the above technical problems and to provide a novel stilbene derivative suitable as a charge transport 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 prior art.

[0008]

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, Compounds having no substituent at one phenyl group in the diphenylamino group and having a substituent at the 2,3-, 2,5- or 2,6-position of the other phenyl group, or only at the 2-position, The present inventors have found a new fact that the stilbene derivative has higher compatibility with the binder resin and higher charge mobility than the stilbene derivative, and has completed the present invention.

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

[0010]

Embedded image (Wherein, R ¹ and R ³ are the same or different and each may be an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent or a substituent An alkoxy group which may have R ² and R ⁴
Represents the same or different and represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent. Provided that the substitution position of R ² and R ⁴ is 4 (para)
R ² and R ⁴ are hydrogen atoms. ).

The stilbene derivative of the present invention represented by the above general formula (1) is a compound not specifically disclosed in the above-mentioned JP-A-7-244389 and JP-A-50-31773, Such a stilbene derivative (1) is used as a charge (hole) transport agent in an electrophotographic photoreceptor because it has higher compatibility with a binder resin and higher charge mobility than the compounds specifically disclosed in the above publication. By using it, a highly sensitive electrophotographic photosensitive member can be obtained.

Further, the present inventors have proposed the stilbene derivative
In the production method of (1), a method for efficiently obtaining the following formyl form of triphenylamine (2), which is a starting material, was studied, and a triphenylamine derivative (5) having a substituent at the 2-position of the phenyl group was obtained. Vilsmeie
r) Formylation by the method, the compound (2) wherein the phenyl group having a substituent among the three phenyl groups of the compound (5) is not formylated, and only the unsubstituted phenyl group is formylated. Of the present invention, which leads to an improvement in the productivity of the stilbene derivative (1), and has completed the present invention.

That is, the stilbene derivative (1) of the present invention
Is produced by the general formula (2):

[0014]

Embedded image (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ² is a hydrogen atom.) And a formylated triphenylamine derivative represented by the general formula (3):

[0015]

Embedded image Characterized by reacting with a bisphosphate derivative represented by the formula:

The formylated triphenylamine derivative (2) used in the production method of the present invention has the general formula (4)
:

[0017]

Embedded image (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ² is a hydrogen atom) by reacting iodobenzene with the aniline derivative represented by the general formula (5):

[0018]

Embedded image (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ² is a hydrogen atom), and the compound (5) is obtained by formylating the compound (5) by the Vilsmeier method.

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

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 above general formula (1). It is characterized by containing.

The electrophotographic photoreceptor of the present invention has the general formula
Since the photosensitive layer contains the stilbene derivative represented by (1), the speed of transporting the charges (holes) generated by the charge generating agent is high, that is, the charge mobility is high, and the light during charging and exposure is high. Excellent sensitivity. 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 above general formula (1), a charge generating agent and an electron transporting agent.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a stilbene derivative of the present invention
(1) will be described in detail.

In the above general formula (1), examples of the alkyl group corresponding to R ¹ , R ² , R ³ and R ⁴ include methyl,
Examples thereof include an alkyl group having 1 to 6 carbon atoms such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl and hexyl. Among them, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
An alkyl group having 1 to 4 carbon atoms such as s-butyl and t-butyl is preferred.

The alkyl groups corresponding to R ¹ , R ² , R ³ and R ⁴ may have a substituent, specifically, a hydroxyalkyl group, an alkoxyalkyl group, a monoalkylaminoalkyl group, Examples include a dialkylaminoalkyl group, a halogen-substituted alkyl group, an alkoxycarbonylalkyl group, a carboxyalkyl group, an alkanoyloxyalkyl group, and an aminoalkyl group.

In particular, in the stilbene derivative (1) of the present invention, from the viewpoint of increasing the charge mobility, an alkyl having an electron-donating group such as an alkoxy group, a monoalkylamino group, an amino group or a dialkylamino group as a substituent. Groups are preferred.

Examples of the hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 1,1-
Dimethyl-2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-hydroxybutyl,
Examples thereof include hydroxyalkyl groups having 1 to 6 carbon atoms in the alkyl portion, such as 1-hydroxypentyl and 6-hydroxyhexyl.

Examples of the alkoxyalkyl group include methoxymethyl, methoxyethyl, methoxybutyl,
Ethoxyhexyl, ethoxymethyl, butoxyethyl,
t-butoxyhexyl, hexyloxymethyl and the like,
An alkoxyalkyl group having 1 to 6 carbon atoms in both the alkyl portion and the alkoxy portion is exemplified.

Examples of the monoalkylaminoalkyl group include methylaminomethyl, ethylaminomethyl,
Hexylaminomethyl, ethylaminoethyl, hexylaminoethyl, methylaminopropyl, butylaminopropyl, methylaminobutyl, ethylaminobutyl, hexylaminobutyl, methylaminohexyl, ethylaminohexyl, butylaminohexyl, hexylaminohexyl, etc. Examples thereof include an alkylaminoalkyl group having 1 to 6 carbon atoms in the alkyl portion.

Examples of the dialkylaminoalkyl group include dimethylaminomethyl, diethylaminomethyl, dihexylaminomethyl, diethylaminoethyl,
Dihexylaminoethyl, dimethylaminopropyl, dibutylaminopropyl, dimethylaminobutyl, diethylaminobutyl, dihexylaminobutyl, dimethylaminohexyl, diethylaminohexyl, dibutylaminohexyl, dihexylaminohexyl, etc. Certain dialkylaminoalkyl groups are mentioned.

Examples of the above alkoxycarbonylalkyl group include methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylhexyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, pentyloxycarbonylmethyl, Both alkyl and alkoxy moieties, such as hexylcarbonylmethyl, hexylcarbonylbutyl, and hexylcarbonylhexyl, have 1 carbon atom.
To 6 are alkoxycarbonylalkyl groups.

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. Can be

Examples of the halogen-substituted alkyl group include monochloromethyl, monobromomethyl, monoiodomethyl, monofluoromethyl, dichloromethyl, dibromomethyl, diiodomethyl, difluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, trifluoromethyl Carbon substituted with 1 to 3 halogen atoms, such as methyl, monochloroethyl, monobromoethyl, monoiodoethyl, monofluoroethyl, dibromobutyl, diiodobutyl, difluorobutyl, chlorhexyl, bromohexyl, iodohexyl, fluorohexyl, etc. And alkyl groups of formulas (1) to (6).

The alkanoyloxyalkyl group includes an alkanoyl moiety having 2 to 6 carbon atoms, such as acetoxymethyl, 2-acetoxyethyl, propionyloxymethyl, 1-hexanoyloxy-2-methylpentyl; And an alkanoyloxy group having 6 alkyl moieties.

Examples of the aminoalkyl group include aminoalkyl groups having 1 to 6 carbon atoms in the alkyl portion thereof, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl and aminohexyl.

The alkoxy group corresponding to R ¹ , R ² , R ³ and R ⁴ includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, pentyloxy, hexyloxy and the like having 1 to 1 carbon atoms. 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 the above-mentioned alkyl group such as a hydroxyl group, a carboxyl group, and an alkanoyloxy group.

The aryl group corresponding to R ¹ and R ³ includes, for example, phenyl, naphthyl, anthryl, phenanthryl and the like.

The aralkyl groups corresponding to R ¹ and R ³ include, for example, benzyl, 1-phenylethyl, 3
And aralkyl groups having 1 to 6 carbon atoms in the alkyl moiety such as -phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and 6-phenylhexyl.

The above aryl group and 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. other,
Examples thereof include an alkyl group which may have a substituent having 1 to 6 carbon atoms and an alkoxy group which may have a substituent having 1 to 6 carbon atoms, as described above. In addition, the substitution positions of these substituents are not particularly limited.

The stilbene derivative (1) of the present invention has the following general formula (11) depending on the substitution position on the central benzene ring.
To (13), and in particular, a stilbene derivative represented by the general formula (11) or (12) is preferably used.

[0041]

Embedded image (Wherein, R ^{1 to} R ⁴ are the same 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 in Table 1 below. ~ 2
Shown in In Tables 1 and 2, compounds having a compound number starting with "11-" are stilbene derivatives contained in the general formula (11), and compounds having a compound number starting with "12-" are represented by the general formula (1
It is a stilbene derivative included in 2).

In Tables 1-2, 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 t-butyl group, MeO is a methoxy group, and E is a methoxy group.
tO represents an ethoxy group, Ph represents a phenyl group, and Bzl represents a benzyl group.

[0043]

[Table 1]

[0044]

[Table 2] The method for synthesizing the stilbene derivative (1) of the present invention is described by R ¹ and R
^{The case where 3} is the same group and R ² and R ⁴ are the same group will be described as an example.

Reaction formula (I):

[0046]

Embedded image (In the formula, R ¹ and R ² are the same as described above.) In this reaction, a formyl derivative of triphenylamine represented by the general formula (2) and a bisphosphate ester derivative (3) are mixed with a suitable anhydrous solvent. By reacting in the presence of a base,
The stilbene derivative of the present invention represented by the general formula (1-a) is obtained.

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. And aromatic hydrocarbons such as toluene.

Examples of the base include sodium alkoxides such as sodium methoxide and metal hydrides such as sodium hydride.

The amount of the base to be used is at least 2 to 4 times, preferably 2 to 2.5 times the molar amount of the bisphosphate ester derivative (3).

The amount of the compound (2) used is 1.8 to 2.5 times, preferably 1.95 to 2.05 times the molar amount of the bisphosphate derivative (3). The reaction is usually performed at -10 to 25 ° C, and is completed in about 3 to 12 hours.

Reaction formula (II):

[0052]

Embedded image (Wherein R ¹ and R ² are the same as described above.) This reaction is carried out by reacting an aniline derivative (4) with iodobenzene (90).
Is added to nitrobenzene, and reacted with a catalyst such as anhydrous potassium carbonate or copper to obtain a triphenylamine derivative (5) .Then, the triphenylamine derivative (5) is formylated by the Vilsmeier method. As a result, a formyl derivative (2) of triphenylamine, which is a starting material of the above reaction formula (I), is obtained.

The aniline derivative (4) and iodobenzene
The ratio of use with (90) is from 1: 1.7 to 3, preferably from 1: 1.8 to 2.2, in a molar ratio. The reaction is usually 160-
The reaction is performed at 220 ° C. and is completed in about 4 to 30 hours.

The reagent (Vilsmeier reagent) used in the above-mentioned Vilsmeier method includes (i) a halogenating agent such as phosphorus oxychloride, phosgene, oxalyl chloride, thionyl chloride, triphenylphosphine-bromine, hexachlorotriphosphazatriene; (ii) N, N-dimethylformamide (DMF), N-methylformanilide (MFA), N
-Formylmorpholine, N, N-diisopropylformamide and the like. In particular, in the present invention, phosphorus oxychloride and DM which can also be used as a solvent are used.
A combination with F is preferably used.

In the preparation of the Vilsmeier reagent,
(i) and (ii) are usually used in a molar ratio of 1: 1 to 2,
Preferably it is 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 performed at 40 to 80 ° C., and is completed in about 2 to 5 hours.

In the stilbene derivative (1) of the present invention, when synthesizing a stilbene derivative (1-x) in which R ¹ and / or R ² has a substituent, for example, R ¹ is a hydroxyalkyl group. May be used to synthesize a stilbene derivative (1-x) using an aniline derivative (4-x) having a hydroxyalkyl group as a starting material.
After synthesizing a stilbene derivative (1-xx) in which ¹ is an alkyl group, the alkyl group is subjected to a conventional method (eg, oxidation)
May be converted to a hydroxyalkyl group to synthesize the stilbene derivative (1-x).

Reaction formula (III):

[0059]

Embedded image This reaction is carried out by reacting α, α'-dichloroxylene (91) with a phosphite triester in a solvent-free or suitable solvent to obtain a bisphosphate ester derivative as a starting material in the above reaction formula (I). (3) is obtained. that time,
Addition of the tertiary amine removes the alkyl halide from the reaction system and promotes the reaction.

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 , Toluene and other aromatic hydrocarbons, and dimethylformamide.

The tertiary amine includes, for example, triethylamine, tributylamine, pyridine, 4- (dimethylamino) pyridine and the like.

The amount of the phosphite triester to be used with respect to α, α'-dichloroxylene (91) is at least 2 times, preferably 2 to 2.4 times. The reaction is usually performed at 80 to 150 ° C., and is completed in about 1 to 4 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, a monophosphate ester derivative may be used in place of the bisphosphate ester derivative (3) in the formyl form of triphenylamine having a different group. It is synthesized by reacting with (2).

Specifically, as shown in the following reaction formula (IV), first, a monophosphoric ester (93) was obtained by reacting a methyl benzyl chloride (92) with a phosphite triester.
Then, formyl form of the above triphenylamine
(2) is reacted to obtain a monostilbene derivative (94), which is further chlorinated to obtain a compound (95).

Reaction formula (IV):

[0066]

Embedded image (In the formula, R ¹ and R ² are the same as described above.) Then, as shown in the following reaction formula (V), the compound (95)
To react with phosphite triester to obtain compound (96),
The stilbene derivative (1-b) is obtained by reacting this with the formyl derivative of triphenylamine (2 ′).

Reaction formula (V):

[0068]

Embedded image (In the formula, R ^{1 to} R ⁴ are the same as described above.) The stilbene derivative represented by the general formula (1) has a high charge mobility, that is, a high hole transport ability as described above. Thus, it can be suitably used as a hole transport 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 the general formula
A photosensitive layer containing a stilbene derivative represented by (1),
It is 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 is obtained by dissolving or dispersing a stilbene derivative (hole transporting agent) represented by the general formula (1), a charge generating agent, a binder resin, and, if necessary, an electron transporting agent in a suitable solvent. It is formed by applying the applied coating liquid on a conductive substrate and drying it. 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 laminate type photoreceptor, a charge generating layer containing a charge generating agent is first formed on a conductive substrate by means such as vapor deposition or coating, and then the general formula ( 1) A coating liquid containing at least one stilbene derivative (hole transporting agent) represented by the formula (1) and a binder resin is applied and dried to form a charge transporting 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. .

The positive / negative charging type is selected depending on the order of forming the charge generating layer and the charge transporting layer and the type of the charge transporting agent used for the charge transporting layer. 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.

In the laminated electrophotographic photosensitive member of the present invention, the residual potential of the photosensitive member is greatly reduced as compared with the conventional laminated electrophotographic photosensitive member using a stilbene derivative as a hole transporting agent, and the sensitivity is low. Has improved.

As described above, the electrophotographic photoreceptor of the present invention can be applied to both a single-layer type and a laminated type. In particular, it 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 of being able to suppress film defects at the time of forming a layer, reducing the interface between layers, and improving optical characteristics.

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

[0080]

Embedded image (CG2) Oxotitanyl phthalocyanine

[0081]

Embedded image (CG3) Perylene pigment

[0082]

Embedded image (In the formula, 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

[0083]

Embedded image [Wherein Cp ¹ and Cp ² represent the same or different coupler residues, and Q represents the following formula:

[0084]

Embedded image (In the formula, 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. Ω is 0 or 1.
Is shown. )

[0085]

Embedded image (In the formula, R ^g4 and R ^g5 are the same or different and 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.)

[0086]

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

[0087]

Embedded image Or

[0088]

Embedded image ( ^Wherein R ^g7 , R ^g8 and R ^g9 are the same or different,
A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom,
It represents an alkoxy group, an aryl group or an aralkyl group. ). (CG5) dithioketopyrrolopyrrole pigment

[0089]

Embedded image ( ^Wherein , R ^g10 and R ^g11 are the same or different and 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

[0090]

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

[0091]

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

[0092]

Embedded image ( ^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

[0093]

Embedded image (Wherein Cp ³ , Cp ⁴ and Cp ⁵ are the same or different and represent a coupler residue.) (CG10) Indigo pigment

[0094]

Embedded image ( ^Wherein , 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

[0095]

Embedded image (In the formula, 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

[0096]

Embedded image ( ^Wherein , R ^g28 and R ^g29 are the same or different and 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. )) In the charge generating agent exemplified above, the alkyl group includes
The same groups as described above can be mentioned. 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.

As the alkoxy group and the aryl group,
The same groups as described above can be mentioned. Examples of the alkanoyl group include formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl and the like. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, pyrrolidinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, 2H-imidazolyl, pyrazolyl, triazolyl,
Examples include tetrazolyl, pyranyl, pyridyl, piperidyl, piperidino, 3-morpholinyl, morpholino, thiazolyl and the like. Further, it may be a heterocyclic group condensed with an aromatic ring. 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, and a group having 1 to 1 carbon atoms.
Examples thereof include an alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms which may have an aryl group.

Cp ¹ , Cp ² , Cp ³ , Cp ⁴ and Cp
The coupler residue represented by p ^5, for example, groups represented by the following formulas (Cp-1) ~ (Cp -11) and the like.

[0101]

Embedded image

[0102]

Embedded image 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, a carbonyl group and a carboxyl group. It may have a group.

R ^g33 represents an atomic group necessary for condensing with a benzene ring to form an aromatic ring, a polycyclic hydrocarbon or a heterocyclic 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 represents a group represented by the following formula (Cp-1) to (Cp-) together with a divalent chain hydrocarbon group or an aromatic hydrocarbon group.
11) represents an atomic group necessary for forming a heterocyclic ring together with the two nitrogen atoms in the ring, 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 R ^g33 , ^examples of the atomic group necessary for condensing with the benzene ring to form an aromatic ring include an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, trimethylene and tetramethylene. Can be

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 above-mentioned alkylene group having 1 to 4 carbon atoms, or a carbazole ring or a benzocarbazole ring. And a dibenzofuran ring.

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 R ^g36 , ^examples of the heterocyclic group include 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. Is raised. These groups may have the same substituents as described above.

In 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, powders of inorganic photoconductive materials such as selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, and the like, pyrylium salts, anthanthrone-based Conventionally known charge generating agents such as pigments, triphenylmethane pigments, sulene 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 charge generating agents exemplified above, in particular, a digital optical image forming apparatus such as a laser beam printer or a facsimile using a light source such as a semiconductor laser includes:
Since a photoreceptor having a sensitivity in a wavelength region of 700 nm or more is required, for example, a phthalocyanine-based pigment such as a metal-free phthalocyanine represented by the general formula (CG1) or an oxotitanyl phthalocyanine represented by the general formula (CG2) is used. It is preferably used. The crystal form of the phthalocyanine pigment is not particularly limited, and various types can be used.

On the other hand, an image forming apparatus of an analog optical system 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, the stilbene derivative of the present invention, which is a hole transport agent, is used.
Along with (1), other conventionally known hole transporting agents may be contained in the photosensitive layer.

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).

[0127]

Embedded image (Wherein, R ^h1 , R ^h2 , R ^h3 , R ^h4 , R ^h5, and R ^h6 are the same or different and are each a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent. Represents an aryl group which may have a group or a substituent, and a and b
Represents the same or different and represents an integer of 0 to 4, c, d, e
And f are the same or different and each represents an integer of 0 to 5. However, when a, b, c, d, e or f is 2 or more, each R
^h1 , ^Rh2 , ^Rh3 , ^Rh4 , ^Rh5 and ^Rh6 may be different. )

[0128]

Embedded image (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 or a substituent Represents an aryl group which may have a group, 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, provided that g, h, i, and When j or k is 2 or more, each of R ^h7 , R ^h8 , R ^h9 , R ^h10 and R
^h11 may be different. )

[0129]

Embedded image(Where R^h12, R^h13, R^h14And R^h15Is the same
Or a halogen atom, an atom which may have a substituent
Alkyl group, alkoxy group which may have a substituent or
The following shows an aryl group which may have a substituent. R^h16Is haloge
, A cyano group, a nitro group, an
Alkyl group, alkoxy group which may have a substituent or
The following shows an aryl group which may have a substituent. m, n, o and
And p are the same or different and each represents an integer of 0 to 5. q is
Shows an integer of 0 to 6. Where m, n, o, p or q is
When 2 or more, each R^h12, R^h13, R^h14, R^h15And
And R ^h16May be different. )

[0130]

Embedded image ( ^Wherein R ^h17 , R ^h18 , R ^h19 and R ^h20 are the same or different and each have a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. And r, s, t and u are the same or different and each represents an integer of 0 to 5, provided that when r, s, t or u is 2 or more, each of R ^h17 , R
^h18, R ^h19 and R ^h20 may be different. )

[0131]

Embedded image (Wherein 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 are a hydrogen atom, an alkyl A group or an aryl group.)

[0132]

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

[0133]

Embedded image (In the formula, R ^h30 , R ^h31 , R ^h32 and R ^h33 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.)

[0134]

Embedded image ( ^Wherein R ^h34 , R ^h35 , R ^h36 , R ^h37 and R ^h38
Represents the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. )

[0135]

Embedded image ( ^Wherein R ^h39 represents a hydrogen atom or an alkyl group;
^h40, R ^h41 and R ^{h4 2} are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. )

[0136]

Embedded image (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.)

[0137]

Embedded image (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 each represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. )

[0138]

Embedded image(Where R^h50, R^h51, R^h52, R^h53, R^h54And
And R^h55May be the same or different and may have a substituent
An alkyl group, an alkoxy group which may have a substituent or
The following shows an aryl group which may have a substituent. α is 1 to 10
And v, w, x, y, z and β are the same or
Represents an integer of 0 to 2 differently. Where v, w, x,
When y, z or β is 2, each R^h50, R^h51,
R^h52, R^h53, R ^h54And R^h55Is different
Good. )

[0139]

Embedded image ^Wherein R ^h56 , R ^h57 , R ^h58 and R ^h59 are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and Φ represents the following formula:

[0140]

Embedded image (Φ-1), (Φ-2) or (Φ-3)
Is shown. 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.

The substituents which may be substituted on the above groups include:
For example, halogen atom, amino group, hydroxyl group, carboxyl group which may be esterified, cyano group, carbon number 1
Examples thereof include an alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms which may have an aryl group. The substitution position of the substituent is not particularly limited.

In the present invention, a conventionally known hole transport material, that is, 2,5-di (4-methylamino) is used together with or instead of the above-described hole transport agents (HT1) to (HT13). 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 hole transporting agent may be used, or two or more hole transporting agents 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,
Examples include compounds represented by the following general formulas (ET1) to (ET17).

[0145]

Embedded image (Wherein, R ^e1 , R ^e2 , R ^e3 , R ^e4, and R ^e5 are the same or different and are a hydrogen 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, an aralkyl group which may have a substituent, a phenoxy group which may have a substituent or a halogen atom.)

[0146]

Embedded image (In the formula, ^{Re 6} represents an alkyl group, ^{Re 7} represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, an aryl group optionally having a substituent, Represents an aralkyl group, a halogen atom or a halogenated alkyl group, which may be an integer of 0 to 5. However, when γ is 2 or more, each ^{Re 7} may be different from each other.)

[0147]

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

[0148]

Embedded image (In the formula, ^Re10 represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, a halogenated alkyl group, or a halogen atom. Ζ represents an integer of 0 to 4, and η represents an integer of 0 to 5.
However, when η is 2 or more, each ^{Re 10} may be different. )

[0149]

Embedded image (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.)

[0150]

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

[0151]

Embedded image ( ^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, a phenyl group which may have a substituent, an alkoxycarbonyl group, an N-alkylcarbamoyl group, a cyano group or a nitro group. λ shows the integer of 0-3. However, when λ is 2 or more, each ^{Re e15} may be different from each other. )

[0152]

Embedded image (In the formula, θ represents an integer of 1 to 2.)

[0153]

Embedded image (In the formula, 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. Ν and ξ are integers of 0 to 3. are shown. However, when ν or ξ is 2 or more, each R ^e16 and R ^e17 may be different from each other.)

[0154]

Embedded image (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.)

[0155]

Embedded image (Wherein, ^{Re 20} represents an amino group, a dialkylamino group, an alkoxy group, an alkyl group or a phenyl group, and π represents 1
2 to 2. However, when π is 2, each R ^{e2 0} may be different from each other. )

[0156]

Embedded image (Wherein, ^{Re 21} represents a hydrogen atom, an alkyl group, an aryl group,
It represents an alkoxy group or an aralkyl group. )

[0157]

Embedded image (In the formula, ^Re22 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. μ represents an integer of 0 to 3.
However, when μ is 2 or more, each ^{Re 22} may be different from each other. )

[0158]

Embedded image (Wherein, R ^e23 represents an aryl group which may have an alkyl group or a substituted group may have a substituent, R ^e24 represents an alkyl group which may have a substituent, a substituent be aryl group or a group:. R ^E24A in the group represented by -O-R ^E24A indicates an aryl group which may have an alkyl group or a substituted group may have a substituent).

[0159]

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

[0160]

Embedded image (In the formula, ^{Re 32} and ^{Re 33} are the same or different and represent 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.)

[0161]

Embedded image ^Wherein R ^e34 , R ^e35 , R ^e36 and R ^e37 are the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a cycloalkyl group or an amino group, provided that R ^e34 , R ^At least two of ^e35 , ^Re36 , and ^Re37 are the same groups that are not hydrogen atoms.) In the above-described electron transporting agent, 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.

As the fused polycyclic group, for example, 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. N-
Examples of the 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 a carbon atom having 1 to 6 carbon atoms. Examples thereof include an alkoxy group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms which may have an aryl group. 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 for 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-
Thermoplastic resins such as vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin; silicone resin, epoxy resin , A phenol resin, a urea resin, a melamine resin, other thermosetting resins having a cross-linking property, and resins such as a photo-curing resin such as an epoxy acrylate and a urethane-acrylate.

In the photosensitive layer, in addition to the above components, various additives known in the art, such as an antioxidant, a radical scavenger, a singlet quencher, and an ultraviolet absorber, as long as the electrophotographic properties 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) (hole transporting agent) of the present invention may be blended 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 crystallize. 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 laminate type 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 2 to 100 μm, preferably about 5 to 50 μm.

In a single-layer type photoreceptor, between the conductive substrate and the photosensitive layer, and in a laminated type photoreceptor, between the conductive substrate and the charge generation layer, and between the conductive substrate and the charge transport layer. A barrier layer may be formed between the charge generation layer and the charge transport layer as long as the characteristics of the photoconductor 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 shape of the conductive substrate may be sheet-like or drum-like depending on the structure of the image forming apparatus to be used, and the substrate itself has conductivity or the surface of the substrate has conductivity. 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, a charge generating agent, a charge transporting agent, a binder resin, etc., together with a suitable solvent, may be used in a known manner, for example, a roll mill, a ball mill, an attritor, a paint, or the like. What is necessary is just to disperse and mix using a shaker, an ultrasonic disperser, etc., to prepare a dispersion liquid, apply this by a well-known means, and to 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 carbons 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.

[0180]

The present invention will be described below with reference to Synthesis Examples, Examples and Comparative Examples.

<< Synthesis of Stilbene Derivative >> Reference Example 1 [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: chloroform / hexane mixed solvent) to obtain 28.8 g of the title compound (yield: 85%).

Reference Example 2 [Synthesis of 2-ethyl-6-methyltriphenylamine]
The reaction was carried out in the same manner as in Reference Example 1 except that 6-ethyl-o-toluidine was used in the same molar amount instead of 2,6-dimethylaniline, to obtain 28.1 g of the title compound (yield 79%).

Reference Example 3 [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 was obtained (83% yield).

Reference Example 4 [Synthesis of 2,3-dimethyltriphenylamine] 2,6
The reaction was carried out in the same manner as in Reference Example 1, except that the same molar amount of 2,3-dimethylaniline was used instead of -dimethylaniline,
28.4 g of the title compound were obtained (yield 84%).

Reference Example 5 [Synthesis of 2-ethyltriphenylamine] The reaction was carried out in the same manner as in Reference Example 1 except that the same molar amount of 2-ethylaniline was used instead of 2,6-dimethylaniline to give the title compound 2
6.7 g was obtained (79% yield).

Reference Example 6 [Synthesis of 2,6-dimethyl-4'-formyltriphenylamine] 28 g of 2,6-dimethyltriphenylamine
(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 7 [Synthesis of 2-ethyl-6-methyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2-ethyl-6-methyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Reference Example 6 except that the compound was used, to obtain 28.2 g of the title compound (yield: 87%).

Reference Example 8 [Synthesis of 2,6-diethyl-4'-formyltriphenylamine] Except that 2,6-diethyltriphenylamine was used in the same molar amount instead of 2,6-dimethyltriphenylamine. The reaction was carried out in the same manner as in Reference Example 6 to give the title compound 2
7.1 g was obtained (80% yield).

Reference Example 9 [Synthesis of 2,3-dimethyl-4'-formyltriphenylamine] Except that 2,3-dimethyltriphenylamine was used in the same molar amount in place of 2,6-dimethyltriphenylamine. The reaction was carried out in the same manner as in Reference Example 6 to give the title compound 2
7.5 g were obtained (89% yield).

Reference Example 10 [Synthesis of 2-ethyl-4'-formyltriphenylamine] Instead of 2,6-dimethyltriphenylamine, 2-
The reaction was carried out in the same manner as in Reference Example 6 except that the same molar amount of ethyltriphenylamine was used to obtain 24.8 g of the title compound (yield: 80%).

Reference Example 11 [Synthesis of bisphosphate ester] Triethyl phosphate and p-
Bisphosphate ester derivatives represented by the following formula (3p) were obtained from xylylene dichloride. Further, from triethyl phosphate and m-xylylene dichloride, the following formula (3
A bisphosphate derivative represented by m) was obtained.

[0192]

Embedded image Reference Example 12 [Synthesis of 2-methoxytriphenylamine] The compound can be synthesized by carrying out the reaction in the same manner as in Reference Example 1 except that o-anisidine is used in the same molar amount instead of 2,6-dimethylaniline.

Reference Example 13 [Synthesis of 2-ethoxytriphenylamine] The synthesis was carried out in the same manner as in Reference Example 1 except that the same molar amount of o-phenetidine was used instead of 2,6-dimethylaniline. Can be.

Reference Example 14 [Synthesis of 2-methoxy-6-methyl-triphenylamine] Instead of 2,6-dimethylaniline, 2-methoxy-
The compound can be synthesized by performing a reaction in the same manner as in Reference Example 1 using 6-methylaniline in the same molar amount.

Reference Example 15 [Synthesis of 2-methoxy-5-methyl-triphenylamine] Instead of 2,6-dimethylaniline, 2-methoxy-
It can be synthesized by performing the reaction in the same manner as in Reference Example 1 using the same molar amount of 5-methylaniline.

Reference Example 16 [Synthesis of 5-methoxy-2-methyl-triphenylamine] Instead of 2,6-dimethylaniline, 5-methoxy-
It can be synthesized by carrying out the reaction in the same manner as in Reference Example 1 using the same molar amount of 2-methylaniline.

Reference Example 17 [Synthesis of 2-methoxy-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2
The compound can be synthesized by performing a reaction in the same manner as in Reference Example 6 using the same molar amount of -methoxytriphenylamine.

Reference Example 18 [Synthesis of 2-ethoxy-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2
-Ethoxytriphenylamine can be synthesized by performing a reaction in the same molar amount as in Reference Example 6.

Reference Example 19 [Synthesis of 2-methoxy-6-methyl-4'-formyltriphenylamine] 2-methoxy-6-methyl-triphenylamine was replaced with 2,6-dimethyltriphenylamine in the same mole. The compound can be synthesized by carrying out a reaction in the same manner as in Reference Example 6 using the above amounts.

Reference Example 20 [Synthesis of 2-methoxy-5-methyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 2-methoxy-5-methyl-triphenylamine was used in the same molar amount. The compound can be synthesized by carrying out a reaction in the same manner as in Reference Example 6 using the above amounts.

Reference Example 21 [Synthesis of 5-methoxy-2-methyl-4'-formyltriphenylamine] In place of 2,6-dimethyltriphenylamine, 5-methoxy-2-methyl-triphenylamine was equimolar. The compound can be synthesized by carrying out a reaction in the same manner as in Reference Example 6 using the above amounts. Synthesis Example 1 [Synthesis of stilbene derivative (11-2)] 5.9 g of bisphosphate ester represented by the above formula (3p) (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. 9.5 g of 2,6-dimethyl-4'-formyltriphenylamine dissolved in 50 ml of tetrahydrofuran (3
(1.5 mmol) was added dropwise and reacted at room temperature for about 3 hours. After the reaction, the reaction solution was added to about 2% of a diluted aqueous hydrochloric acid solution (400 ml), and the precipitated crystals were filtered and washed with water. After drying the crystals, silica gel column chromatography (developing solvent:
Purification with a mixed solvent of chloroform / hexane) gave 7.0 g of the stilbene derivative represented by Compound No. 11-2 in Table 1 (66% yield).

Melting point: 190-192 ° C. The ¹ H-NMR spectrum of the above stilbene derivative (11-2) is shown in FIG. 1, and the infrared absorption spectrum is shown in FIG. Synthesis Example 2 [Synthesis of stilbene derivative (11-6)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 2-ethyl-6-methyl-4'-formyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Synthesis Example 1 except that Compound No. 1 was used.
7.2 g of the stilbene derivative represented by 1-6 was obtained (65% yield).

Melting point: 194 ° -197 ° C. The ¹ H-NMR spectrum of the stilbene derivative (11-6) is shown in FIG. 3, and the infrared absorption spectrum is shown in FIG. Synthesis Example 3 [Synthesis of stilbene derivative (11-7)] Instead 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.
8.1 g of the stilbene derivative indicated by
%).

Melting point: 224 to 226 ° C. FIG. 5 shows the ¹ H-NMR spectrum of the above stilbene derivative (11-7), and FIG. 6 shows the infrared absorption spectrum thereof. Synthesis Example 4 [Synthesis of stilbene derivative (12-3)] In place of 2,6-dimethyl-4′-formyltriphenylamine, 2,3-dimethyl-4′-formyltriphenylamine was used, and The reaction was carried out in the same manner as in Synthesis Example 1 except that the bisphosphate ester represented by the above formula (3m) was used in the same molar amount instead of the bisphosphate ester represented by the formula (3m). 6.5 g of the stilbene derivative represented by -3 was obtained (yield: 61%).

Melting point: 93-96 ° C. FIG. 7 shows an infrared absorption spectrum of the stilbene derivative (12-3). Synthesis Example 5 [Synthesis of stilbene derivative (12-5)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2-ethyl-4'-formyltriphenylamine was used, and in the above formula (3p) The reaction was carried out in the same manner as in Synthesis Example 1 except that the bisphosphate ester represented by the above formula (3m) was used in the same molar amount instead of the bisphosphate ester represented by
5.9 g of the stilbene derivative represented by the compound number 12-5 in Table 2 was obtained (yield: 56%).

Melting point: 92-95 ° C. FIG. 8 shows an infrared absorption spectrum of the stilbene derivative (12-5). Synthesis Example 6 [Synthesis of stilbene derivative (11-14)] Synthetic example using 2-methoxy-4'-formyltriphenylamine instead of 2,6-dimethyl-4'-formyltriphenylamine in the same molar amount By conducting the reaction in the same manner as in No. 1, Compound Nos. 11-14 in Table 1 above were obtained.
Can be obtained. Synthesis Example 7 [Synthesis of stilbene derivative (11-15)] Synthesis example using 2-ethoxy-4'-formyltriphenylamine in place of 2,6-dimethyl-4'-formyltriphenylamine in the same molar amount The reaction was carried out in the same manner as in No. 1 to give Compound Nos. 11-15 in Table 1 above.
Can be obtained. Synthesis Example 8 [Synthesis of stilbene derivative (11-16)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 2-methoxy-6-methyl-4'-formyltriphenylamine was used in the same molar amount. By performing a reaction in the same manner as in Synthesis Example 1, a stilbene derivative represented by Compound No. 11-16 in Table 1 can be obtained. Synthesis Example 9 [Synthesis of stilbene derivative (11-17)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 2-methoxy-5-methyl-4'-formyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Synthesis Example 1 to obtain a stilbene derivative represented by Compound No. 11-17 in Table 1 above. Synthesis Example 10 [Synthesis of stilbene derivative (11-18)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 5-methoxy-2-methyl-4'-formyltriphenylamine was used in the same molar amount. The reaction was carried out in the same manner as in Synthesis Example 1 to obtain a stilbene derivative represented by Compound No. 11-18 in Table 1 above. Synthesis Example 11 [Synthesis of stilbene derivative (12-14)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2-methoxy-4'-formyltriphenylamine was used. By performing the reaction in the same manner as in Synthesis Example 1 using the same molar amount of the bisphosphate ester represented by the above formula (3m) in place of the bisphosphate ester represented by the above formula, the compound No. 12-14 in Table 2 was used. The stilbene derivative shown can be obtained. Synthesis Example 12 [Synthesis of stilbene derivative (12-15)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2-ethoxy-4'-formyltriphenylamine was used, and in the above formula (3p) By performing the reaction in the same manner as in Synthesis Example 1 by using the same molar amount of the bisphosphate ester represented by the above formula (3m) instead of the bisphosphate ester represented by the above formula, the compound Nos. The stilbene derivative shown can be obtained. Synthesis Example 13 [Synthesis of stilbene derivative (12-16)] In place of 2,6-dimethyl-4'-formyltriphenylamine, 2-methoxy-6-methyl-4'-formyltriphenylamine was used. By performing the reaction in the same manner as in Synthesis Example 1 using the same molar amount of the bisphosphate ester represented by the above formula (3m) instead of the bisphosphate ester represented by the formula (3p), Number 12-
The stilbene derivative represented by No. 16 can be obtained. Synthesis Example 14 [Synthesis of stilbene derivative (12-17)] 2-methoxy-5-methyl-4'-formyltriphenylamine was used in place of 2,6-dimethyl-4'-formyltriphenylamine, and By performing the reaction in the same manner as in Synthesis Example 1 using the same molar amount of the bisphosphate ester represented by the above formula (3m) instead of the bisphosphate ester represented by the formula (3p), Number 12-
A stilbene derivative represented by 17 can be obtained. Synthesis Example 15 [Synthesis of stilbene derivative (12-18)] Instead of 2,6-dimethyl-4'-formyltriphenylamine, 5-methoxy-2-methyl-4'-formyltriphenylamine was used, and By performing the reaction in the same manner as in Synthesis Example 1 using the same molar amount of the bisphosphate ester represented by the above formula (3m) instead of the bisphosphate ester represented by the formula (3p), Number 12-
A stilbene derivative represented by 18 can be obtained.

<< Manufacture 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 stilbene derivative represented by the compound number (11-2) in Table 1 was used as the hole transporting agent.

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 A single-layer photosensitive material for a digital light source was produced in the same manner as in Example 1 except that the stilbene derivative represented by the compound number (11-6) in Table 1 was used as the hole transporting agent. Body manufactured.

Example 3 A single-layer photosensitive material for a digital light source was prepared in the same manner as in Example 1 except that the stilbene derivative represented by the compound number (11-7) in Table 1 was used as the hole transporting agent. Body manufactured.

Example 4 A single-layer photosensitive material for a digital light source was prepared in the same manner as in Example 1 except that the stilbene derivative represented by the compound number (12-3) in Table 1 was used as the hole transporting agent. Body manufactured.

Example 5 A single-layer photosensitive material for a digital light source was prepared in the same manner as in Example 1 except that the stilbene derivative represented by the compound number (12-5) in Table 1 was used as the hole transporting agent. Body manufactured.

Example 6 In the coating solution for a single-layer type photosensitive layer, an electron transporting agent represented by the following formula (ET17-1):

[0214]

Embedded image A single-layer type 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 was mixed.

Example 7 A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 6, except that the stilbene derivative (11-6) was used as the hole transporting agent.

Example 8 A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 6, except that the stilbene derivative (11-7) was used as the hole transporting agent.

Example 9 A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 6, except that the stilbene derivative (12-3) was used as the hole transporting agent.

Example 10 A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Example 6, except that the stilbene derivative (12-5) was used as the hole transporting agent.

Examples 11 to 15 As an electron transporting agent, a compound represented by the formula (ET14-1):

[0220]

Embedded image Example 6 except that the stilbene derivative represented by
In the same manner as in Examples 10 to 10, a single-layer type photoreceptor for a digital light source was manufactured.

Examples 16 to 20 As the electron transporting agent, a compound represented by the formula (ET14-2):

[0222]

Embedded image Example 6 except that the stilbene derivative represented by
In the same manner as in Examples 10 to 10, a single-layer type photoreceptor for a digital light source was manufactured.

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

[0224]

Embedded image 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.

Comparative Example 2 A compound represented by the formula (6-2):

[0226]

Embedded image 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.

Comparative Example 3 As a hole transporting agent, a compound represented by the formula (6-3):

[0228]

Embedded image 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.

The photosensitive members obtained in Examples 1 to 20 and Comparative Examples 1 to 3 were subjected to the following electrical property test (I) to evaluate the electrical properties of each photosensitive member.

Electrical Characteristics Test (I) Using a drum sensitivity tester manufactured by GENTEC
A voltage is applied to the surface of each photoconductor by applying
After charging to 0 ± 20V, the surface potential V_oMeasure (V)
did. Next, the white light of the halogen lamp
Wavelength 780 extracted from the hologram using a band-pass filter
nm monochromatic light (half-width 20 nm, light intensity 8 μJ / c
m^Two) Onto the surface of the photoconductor (irradiation time 1.5 seconds)
And the surface potential V_oThe time it took for the
Measured, half-exposure E_1/2(ΜJ / cm ^Two)
Was. In addition, the surface at the time of 0.5 seconds after the start of exposure
Potential is residual potential V_rIt was measured as (V).

Table 3 shows the types of the charge generating agent, the hole transporting agent and the electron transporting agent used in 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.

[0232]

[Table 3] Examples 21 to 25 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 5, except that G2-1) was used.

Examples 26 to 30 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Examples 6 to 10, except that G2-1) was used.

Examples 31 to 35 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was produced in the same manner as in Examples 11 to 15, except that G2-1) was used.

Examples 36 to 40 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was produced in the same manner as in Examples 16 to 20, except that G2-1) was used.

Comparative Examples 4 to 6 α-oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Comparative Examples 1 to 3, except that G2-1) was used.

Examples 21 to 40 and Comparative Examples 4 to 6
The electrical characteristics test (I) was performed on the photoreceptors obtained in the above, and the electrical characteristics of each photoreceptor were evaluated. Table 4 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.

[0238]

[Table 4] Examples 41 to 45 Y-type oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Examples 1 to 5, except that G2-2) was used.

Examples 46 to 50 Y-type oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was produced in the same manner as in Examples 6 to 10, except that G2-2) was used.

Examples 51 to 55 Y-type oxotitanyl phthalocyanine (C
A single-layer type photoreceptor for a digital light source was manufactured in the same manner as in Examples 11 to 15, except that G2-2) was used.

Examples 56 to 60 Y-type oxotitanyl phthalocyanine (C
A single-layer photoreceptor for a digital light source was manufactured in the same manner as in Examples 16 to 20, except that G2-2) was used.

Comparative Examples 7 to 9 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 3, except that G2-2) was used.

Examples 41 to 60 and Comparative Examples 7 to 9
The electrical characteristics test (I) was performed on the photoreceptors obtained in the above, and the electrical characteristics of each photoreceptor were evaluated. 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.

[0244]

[Table 5] (Laminated photoconductor for digital light source) Example 61 X-type metal-free phthalocyanine (CG1-1) which is a charge generating agent
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, a stilbene derivative which is a hole transporting agent
(11-2) 1 part by weight and binder resin (polycarbonate) 1
The parts by weight were mixed and dispersed in a ball mill together with 10 parts by weight of a solvent (tetrahydrofuran) to prepare a coating liquid for a charge transport layer. Next, this coating solution is 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, thereby producing a laminated photoreceptor for a digital light source. did.

Example 62 A laminated photoconductor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (11-6) was used as the hole transporting agent.

Example 63 A laminated photoconductor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (11-7) was used as the hole transporting agent.

Example 64 A laminated photoreceptor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (12-3) was used as the hole transporting agent.

Example 65 A laminated photoconductor for a digital light source was manufactured in the same manner as in Example 61 except that the stilbene derivative (12-5) was used as the hole transporting agent.

Examples 66-70 α-Oxotitanyl phthalocyanine (C
A laminated photoreceptor for a digital light source was manufactured in the same manner as in Examples 61 to 65 except that G2-1) was used.

Examples 71 to 75 Y-type oxotitanyl phthalocyanine (C
A laminated photoreceptor for a digital light source was manufactured in the same manner as in Examples 61 to 65 except that G2-2) was used.

Comparative Examples 10 to 12 A laminated photoreceptor for a digital light source was produced in the same manner as in Examples 61, 66 and 71 except that the stilbene derivative (6-1) was used as the hole transporting agent.

Examples 61 to 75 and Comparative Examples 10
The following electrical characteristics test (II) was performed on the photoreceptor obtained in Step 12.
And evaluated the electrical characteristics of each photoconductor.

Electrical Characteristics Test (II) Except that the surface of the photoreceptor was charged to -700 ± 20V,
The surface potential V was determined in the same manner as in the electrical characteristic test (I).
_o (V), residual potential V _r (V) and half-exposure amount E _1/2
(ΜJ / cm ² ) was determined.

Table 6 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.

[0256]

[Table 6] (Single-layer type photoconductor for analog light source) Examples 76 to 80 Formula (CG3-1) as a charge generating agent:

[0257]

Embedded image Examples 1 to 5 except that the perylene pigment represented by
A single-layer type photoreceptor for an analog light source was manufactured in the same manner as described above.

Examples 81 to 85 Single-layer photoreceptors for analog light sources were produced in the same manner as in Examples 6 to 10 except that perylene pigment (CG3-1) was used as the charge generator.

Examples 86 to 90 Single-layer photosensitive members for analog light sources were manufactured in the same manner as in Examples 11 to 15, except that perylene pigment (CG3-1) was used as the charge generator.

Examples 91 to 95 Single-layer photosensitive members for analog light sources were manufactured in the same manner as in Examples 15 to 20, except that perylene pigment (CG3-1) was used as the charge generator.

Comparative Examples 13 to 15 Single-layer photoreceptors for analog light sources were produced in the same manner as in Comparative Examples 1 to 3, except that perylene pigment (CG3-1) was used as the charge generator.

Examples 76-95 and Comparative Examples 13-
For the photoreceptor obtained in No. 15, the following electrical property test (II
I) was performed to evaluate the electrical characteristics of each photoconductor.

Electric property test (III) The surface potential V _o (V) and residual electric potential were _{measured 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. The potential V _r (V) and the half-life exposure amount E _1/2 (lux · sec) were determined.

Table 7 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.

[0265]

[Table 7] Examples 96 to 100 As a charge generating agent, a compound represented by the formula (CG4-1):

[0266]

Embedded image Except for using the bisazo pigment represented by
In the same manner as in Example No. 80, a single-layer type photoreceptor for an analog light source was manufactured.

Examples 101 to 105 Single-layer photosensitive members for analog light sources were manufactured in the same manner as in Examples 81 to 85 except that bisazo pigment (CG4-1) was used as the charge generator.

Examples 106 to 110 Single layer type photoreceptors for analog light sources were produced in the same manner as in Examples 86 to 90 except that bisazo pigment (CG4-1) was used as a charge generating agent.

Examples 111 to 115 A single-layer photosensitive member for an analog light source was manufactured in the same manner as in Examples 91 to 95 except that a bisazo pigment (CG4-1) was used as a charge generator.

Comparative Examples 16 to 18 Single-layer photosensitive members for analog light sources were produced in the same manner as in Comparative Examples 13 to 15, except that bisazo pigment (CG4-1) was used as the charge generator.

Examples 96 to 115 and Comparative Example 16
The electrical characteristics test (II
I) was performed to evaluate the electrical characteristics of each photoconductor. Table 8 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.

[0272]

[Table 8] Examples 116 to 120 As a charge generator, a compound represented by the formula (CG4-2):

[0273]

Embedded image Except for using the bisazo pigment represented by
In the same manner as in Example No. 80, a single-layer type photoreceptor for an analog light source was manufactured.

Examples 121 to 125 Single-layer photosensitive members for analog light sources were manufactured in the same manner as in Examples 81 to 85 except that bisazo pigment (CG4-2) was used as the charge generator.

Examples 126 to 130 Single layer type photoreceptors for analog light sources were manufactured in the same manner as in Examples 86 to 90 except that bisazo pigment (CG4-2) was used as the charge generator.

Examples 131 to 135 Single-layer photosensitive members for analog light sources were manufactured in the same manner as in Examples 91 to 95 except that bisazo pigment (CG4-2) was used as the charge generator.

Comparative Examples 19 to 21 Single-layer photoreceptors for analog light sources were produced in the same manner as in Comparative Examples 13 to 15, except that bisazo pigment (CG4-2) was used as the charge generator.

Examples 116 to 135 and Comparative Example 1
The electrical characteristics test (I
II) 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.

[0279]

[Table 9] Examples 136 to 140 Formula (CG4-3) as a charge generating agent:

[0280]

Embedded image Except for using the bisazo pigment represented by
In the same manner as in Example No. 80, a single-layer type photoreceptor for an analog light source was manufactured.

Examples 141 to 145 A single-layer type photoreceptor for an analog light source was manufactured in the same manner as in Examples 81 to 85 except that a bisazo pigment (CG4-3) was used as a charge generator.

Examples 146 to 150 Single layer type photoreceptors for analog light sources were produced in the same manner as in Examples 86 to 90 except that bisazo pigment (CG4-3) was used as the charge generator.

Examples 151 to 155 A single-layer photoreceptor for an analog light source was manufactured in the same manner as in Examples 91 to 95 except that a bisazo pigment (CG4-3) was used as a charge generator.

Comparative Examples 22 to 24 Except that a bisazo pigment (CG4-3) was used as a charge generating agent, single-layer photosensitive members for analog light sources were produced in the same manner as in Comparative Examples 13 to 15.

Examples 136 to 155 and Comparative Example 2
For the photoreceptors obtained in 2 to 24, the electrical characteristics 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.

[0286]

[Table 10] (Laminated Photoconductor for Analog Light Source) Examples 156 to 160 A laminated photoconductor for an analog light source was manufactured in the same manner as in Examples 61 to 65 except that perylene pigment (CG3-1) was used as a charge generating agent. did.

Examples 161 to 165 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 65 except that a bisazo pigment (CG4-1) was used as a charge generator.

Examples 166 to 170 Except that a bisazo pigment (CG4-2) was used as a charge generating agent, a laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 65.

Examples 171 to 175 A laminated photoreceptor for an analog light source was manufactured in the same manner as in Examples 61 to 65 except that a bisazo pigment (CG4-3) was used as a charge generator.

Comparative Examples 25 to 28 Except that the stilbene derivative (6-1) was used as the hole transporting agent, a laminated photoreceptor for an analog light source was produced in the same manner as in Examples 156, 161, 166 and 171. .

Examples 156 to 175 and Comparative Example 2
The following electrical property tests were performed on the photoconductors obtained in 5 to 28.
(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,
The surface potential V was determined in the same manner as in the electrical property test (III).
_o (V), residual potential V _r (V) and half decay exposure amount E _1/2
(Lux · second).

Table 11 shows the types of the charge generating agent and the hole transporting agent used in the above Examples and Comparative Examples, and the test results of the electrical characteristics.

[0294]

[Table 11] Table 3-11 As apparent, electrophotographic photoreceptors of Examples 1 to 175, the smaller the absolute value of the residual potential V _r as compared with the comparative examples corresponding to the embodiments. Further, the half-exposure amount E _1/2
Is also 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.

Further, the stilbene derivatives (11-14) to (11-18) in Synthesis Examples 6 to 10 and the stilbene derivatives (12-14) to (12-18) in Synthesis Examples 11 to 15 were used in Examples described above. In the same manner as in Examples 1 to 175, when electrophotographic photosensitive members (single-layer and laminated photosensitive members for an analog light source, and single-layer and laminated photosensitive members for a digital light source) were manufactured in the same manner as in Examples 1-175 A photoreceptor having excellent sensitivity as in the case of the electrophotographic photoreceptor is obtained.

[0296]

As described in detail above, the stilbene derivative (1) of the present invention has high compatibility with the binder resin and has high charge transport ability (hole transport ability).

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 is a graph showing a ¹ H-NMR spectrum of a stilbene derivative (11-2).

FIG. 2 is a graph showing an infrared absorption spectrum of a stilbene derivative (11-2).

FIG. 3 is a graph showing a ¹ H-NMR spectrum of a stilbene derivative (11-6).

FIG. 4 is a graph showing an infrared absorption spectrum of a stilbene derivative (11-6).

FIG. 5 is a graph showing a ¹ H-NMR spectrum of a stilbene derivative (11-7).

FIG. 6 is a graph showing an infrared absorption spectrum of a stilbene derivative (11-7).

FIG. 7 is a graph showing an infrared absorption spectrum of a stilbene derivative (12-3).

FIG. 8 is a graph showing an infrared absorption spectrum of a stilbene derivative (12-5).

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshio Inagaki 1-2-28 Tamazo, Chuo-ku, Osaka-shi, Osaka F-term in Mita Kogyo Co., Ltd. (reference) 2H068 AA20 AA21 AA31 BA12 BA13 BA63 EA04 4H006 AA01 AA02 AB76 AC22 AC45 AC52

Claims (6)

[Claims] [Claim 1] General formula (1): (Wherein, R ¹ and R ³ are the same or different and each may be an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent or a substituent An alkoxy group which may have R ² and R ⁴
Represents the same or different and represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent. Provided that the substitution position of R ² and R ⁴ is 4 (para)
R ² and R ⁴ are hydrogen atoms. A stilbene derivative represented by). 2. The stilbene derivative according to claim 1, wherein R ³ and R ¹ in the general formula (1) are the same group, and R ⁴ and R ² are the same group. (3) The general formula (2): (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ² is a hydrogen atom.) And a formylated triphenylamine derivative represented by the following 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. The formylated triphenylamine derivative
(2) has the general formula (4): (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ² is a hydrogen atom) by reacting iodobenzene with the aniline derivative represented by the general formula (5): (Wherein, R ¹ is an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an alkoxy group which may have a substituent. R ² represents a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent, provided that when the substitution position of R ² is at the 4 (para) position, ^The method for producing a stilbene derivative according to claim 3, which is obtained by obtaining a triphenylamine derivative represented by the following formula (2), and subjecting this compound (5) to formylation by the Vilsmeier 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. The photosensitive layer is a single-layer photosensitive layer containing a stilbene derivative represented by the general formula (1) according to claim 1 or 2 and a charge generating agent and an electron transporting agent. Item 6. The electrophotographic photosensitive member according to Item 5.