JPH11158165A - Phenothiazine derivative, phenoxazine derivative, charge transport material and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel compound that bears a substituent as an aryl vinyl skeleton and the like on the (substituted) phenothiazine and the (substituted) phenoxazine, shows good solubility in binding polymer and the like and is useful as a charge-transporting material that can form an electro-photographic photoreceptor of high sensitivity with low residual potential. SOLUTION: This compound is represented by formula I [Ar<1> and Ar<2> are each a (substituted) aryl; R<1> and R<2> are each H, a lower alkyl or the like; R<3> is a lower alkyl, a 5-7C alicyclic hydrocarbon or the like; X is S, O; n and m are each 0 or 1], typically 3,7-bis(2',2'-diphenylvinyl)-10-ethylphenothiazine. The compound of formula I is prepared, for example, by reaction of a compound of formula II as 3,7-diformyl-10-ethylphenothiazine with a double molar amount of a compound of formula III (R<4> is a lower alkyl) as diethyl diphenylmethyl phosphite in a solvent in the presence of a base as potassium t-butoxide at room temperature - at about 80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the following general formula (1):

Embedded image (1) (wherein, Ar ¹ and Ar ² may be the same or different, each represents an aryl group which may have a substituent, and R ¹ ,
R ² , which may be the same or different, represents a hydrogen atom, a lower alkyl group, or an aryl group which may have a substituent. R ³ represents a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an aryl group which may have a substituent, an aralkyl group which may have a substituent, X represents a sulfur atom or Represents an oxygen atom. n and m represent an integer of 0 or 1. The present invention relates to a phenothiazine derivative, a phenoxazine derivative, and / or a charge transport material containing the same, and an electrophotographic photoreceptor containing the charge transport material.

[0002]

2. Description of the Related Art In recent years, inorganic photoconductive materials include:
Amorphous silicon, amorphous selenium, cadmium sulfide, zinc oxide, and the like are used, but they are expensive due to difficulty in production, and may be toxic and have problems from the viewpoint of environmental protection. On the other hand, as an organic photoconductor, a form in which the photoconductor is separated into a charge generating material and a charge transporting material, in particular, has been actively proposed (for example,
U.S. Pat. No. 3,791,826). In this method, a high-sensitivity electrophotograph is obtained by using a substance having high generation efficiency of carriers (carriers indicate electric charge, the same applies hereinafter) as a charge generation material and combining a substance having a high charge transport ability as a charge transport material. Photoconductor may be obtained.

[0003] Among these, what is required of the charge transport material is to efficiently receive carriers generated in the charge generation material by light irradiation under the application of an electric field, move the carrier quickly in the photoreceptor layer, and quickly eliminate surface charges. That is. The speed at which carriers move per unit electric field is called carrier mobility. Higher carrier mobility means that carriers move faster in the charge transport layer. This carrier mobility is specific to the charge transport material, and therefore, it is necessary to use a material having a high carrier mobility in order to achieve a high carrier mobility, but it is not yet at a sufficient level. The current situation is that it cannot be said. Further, when the charge transport material is dissolved in an organic solvent together with a binder polymer and applied, it is necessary to form a uniform organic thin film free of crystal precipitation and pinhole formation in the coating film. This is because application of a high electric field to the obtained thin film may cause dielectric breakdown or noise when microcrystals or pinholes are generated.

Further, even if the characteristics of both the charge generating material and the charge transporting material are good, it is efficient to inject carriers from the charge generating material to the charge transporting material, that is, charge injection from the charge generating layer to the charge transporting layer. It is important that things are done well. This charge injection depends on the characteristics of the interface between the charge generating substance (or charge generating layer) and the charge transporting substance (or charge transporting layer), and is not uniform among various substances. As described above, since various conditions are required for the charge transport material, charge transport materials having various characteristics have been developed.

Conventionally, as a charge transporting material, for example, Japanese Patent Application Laid-Open No. Sho 60-175052 discloses the following general formula (A):

Embedded image (A) (wherein, R ⁵ represents an alkyl group containing a substituted alkyl group or an aryl group containing a substituted aryl group, and R ⁶ represents a hydrogen atom, an alkyl group containing a substituted alkyl group, or an aryl group containing a substituted aryl group. And Ar ³ represents an aryl group including a substituted aryl group.), And a compound similar to the above compound (A) is proposed.
It has been proposed in JP-A-62-120346, JP-A-1-217357, JP-A-4-57056, JP-A-4-92663 and the like.

Further, a part of the compound of the present invention is disclosed as an organic electroluminescent device in JP-A-6-271846, and the following compound (B) is described in Examples.

Embedded image (B)

[0007]

SUMMARY OF THE INVENTION
JP-A-4-57056 discloses a binder polymer of the following compound (C).
It is described that some crystals were precipitated during the production of the photoreceptor due to poor solubility in water.

Embedded image (C) At present, the compounds described in JP-A-6-271846 have no known usefulness as an electrophotographic photosensitive member as well as a charge transporting material.

[0008] Recently, the demand for charge transporting materials has been increasing more and more, and accordingly, there is a need for newer materials capable of meeting various conditions. Therefore, it has been desired to develop a new charge transporting material that can exhibit satisfactory electrophotographic characteristics such as high solubility and high solubility in a binder polymer. SUMMARY OF THE INVENTION An object of the present invention is to provide a new charge transporting material which is excellent in various properties such as good solubility, low residual potential when forming an electrophotographic photosensitive member, and high sensitivity.

[0009]

Under these circumstances, the present inventors have conducted intensive studies on various compounds, and as a result, have found that 10-substituted phenothiazines and aryl vinyls at the 3- and 7-positions of the 10-substituted phenoxazines. The following general formula (1) having a skeleton substituent or an arylbutadienyl skeleton substituent

Embedded image (1) (wherein, Ar ¹ and Ar ² may be the same or different, each represents an aryl group which may have a substituent, and R ¹ ,
R ² , which may be the same or different, represents a hydrogen atom, a lower alkyl group, or an aryl group which may have a substituent. R ³ represents a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an aryl group which may have a substituent, an aralkyl group which may have a substituent, X represents a sulfur atom or Represents an oxygen atom. n and m each represent an integer of 0 or 1. The phenothiazine derivative and the phenoxazine derivative represented by the formula (1) can solve the above problems,
The present invention has been completed.

That is, the present inventors have found that the compound (1) has a good solubility in a binder polymer and the like, does not cause precipitation of crystals or formation of pinholes, and a photosensitive material using the compound. The body was found to be sensitive and have low residual potential.

Accordingly, the first aspect of the present invention provides the following general formula (1)

Embedded image (1) (wherein, Ar ¹ and Ar ² may be the same or different, each represents an aryl group which may have a substituent, and R ¹ ,
R ² , which may be the same or different, represents a hydrogen atom, a lower alkyl group, or an aryl group which may have a substituent. R ³ represents a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an aryl group which may have a substituent, an aralkyl group which may have a substituent, X represents a sulfur atom or Represents an oxygen atom. n and m represent an integer of 0 or 1. The present invention relates to a phenothiazine derivative and a phenoxazine derivative represented by the formula:

In the second aspect of the present invention, the compound represented by the general formula (1) (wherein Ar ¹ and Ar ² may be the same or different from each other, and include a lower alkyl group, a lower alkoxy group, a halogen atom, R ¹ represents an aryl group which may have a dialkylamino group, and R ¹ and R ² may be the same or different, and each represents a hydrogen atom, a lower alkyl group, or a lower alkyl group, or a lower alkoxy group. group, a halogen atom, diallyl - arylamino group, an aryl group which may have a dialkylamino group .R ³ is a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, or a lower alkyl group, a lower An alkoxy group, a halogen atom, a diarylamino group,
X represents an aryl group optionally having a dialkylamino group, or an aralkyl group optionally having a benzyl group, a tolylmethyl group, a methoxybenzyl group, or a chlorobenzyl group, and X represents a sulfur atom or an oxygen atom. n and m represent an integer of 0 or 1. )), Relates to a phenothiazine derivative and a phenoxazine derivative in which one of n and m is 1 and the other is 0, or both are 1.

The third invention relates to a charge transport material containing the phenothiazine derivative and the phenoxazine derivative of the first and second inventions represented by the general formula (1).

A fourth aspect of the present invention relates to an electrophotographic photosensitive member containing the charge transport material of the third aspect of the present invention.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound (1) of the present invention, Ar ¹ and Ar ² may be the same or different, and a phenyl group,
In addition to unsubstituted aryl groups such as naphthyl group, lower alkyl groups such as lower alkyl group substituted phenyl group such as ortho tolyl group, metatolyl group, paratolyl group and xylyl group, methoxyphenyl group, ethoxyphenyl group and lower alkoxy group such as propoxyphenyl group Examples include a substituted phenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a halogen-substituted phenyl group of an iodophenyl group, an amino-substituted phenyl group such as a diarylaminophenyl group and a dialkylaminophenyl group. R ¹ and R ² may be the same or different, and each represent a hydrogen atom, a lower alkyl group, or an aryl group which may have a substituent, and the lower alkyl group has 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group and a t-butyl group. Examples of the aryl group which may have a substituent include the same substituent groups as Ar ¹ and Ar ² described above.
R ³ is a lower alkyl group as defined for R ¹ and R ² above, Ar ¹ and A
Other aryl group which may have the same substituents as r ^2, alicyclic hydrocarbon group having a carbon number of 5-7, i.e. a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, further benzyl, tolylmethyl And aralkyl groups which may have a substituent such as a methoxybenzyl group and a chlorobenzyl group.

Preferred specific examples of the compound of the present invention represented by the general formula (1) include the compounds shown in the following Tables 1 to 4, but the compound of the present invention is not limited thereto. In addition, the abbreviation for the substituent in each table,
Each has the following meaning. Me: methyl group, Et: ethyl group, n-Pr: propyl group, i-Pr: iso-propyl group, n-Bu: butyl group, t-Bu: tert-butyl group, s-Bu: sec-
Butyl group, Ph: phenyl group, Naph: naphthyl group,
MeO: methoxy group. The number in each substituent indicates the substitution position, for example, Ph- (2) Me (4) Me
Means a phenyl group having a methyl group at the 2-position and 4-position, for example, 1-Naph means a naphthyl group bonded at the 1-position.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

In the general formula (1) of the present invention, n = m = 0,
The 3,7-bisvinylphenothiazines and 3,7-bisvinylphenoxazines (1a) where Ar ¹ = Ar ² and R ¹ = R ² can be synthesized according to Reaction Scheme 1.

Embedded image Reaction formula 1 (wherein, Ar ¹ , R ¹ , R ³ , and X represent the same meaning as described above, and R ⁴ represents a lower alkyl group)

R ⁴ represents a methyl group, an ethyl group, a propyl group or a butyl group, and a methyl group and an ethyl group are particularly desirable. That is, 10-substituted 3,7-diformylphenothiazine and / or 3,7-diformylphenoxazine (2)
And a 2-fold molar amount of the substituted dialkyl phosphite (3) in the presence of a base at a temperature from room temperature to about 80 ° C. to easily produce the compound. The base used is a metal alkoxide such as sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride and sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, and the amount is based on the substituted dialkyl phosphite (3). It is at least 1 times, preferably 1.1 to 1.5 times. Examples of the solvent include methanol, lower alcohols such as ethanol, ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as toluene and xylene, dimethyl sulfoxide, N, N-dimethylformamide, and N, N An aprotic polar solvent such as -dimethylacetamide, N-methylpyrrolidone, or a mixture thereof can be used. The reaction temperature can be selected in a wide range depending on factors such as the solvent used, the base, and the reactivity of the substrate. For example, 0 ° C. to 150
° C, preferably from room temperature to 80 ° C.

Here, the 10-substituted 3,7-diformylphenothiazine and the 10-substituted 3,7-diformylphenoxazine (2) are obtained by adding a Lewis acid or 10-substituted phenothiazine or 10-substituted phenoxazine (4). It can be obtained by performing a Vielsmeyer-Haak reaction in the presence of a protonic acid. (Reaction formula 2) The amount of the Lewis acid or protonic acid is preferably 1 to 2 times the amount of the 10-substituted 3,7-diformylphenothiazine and the 10-substituted 3,7-diformylphenoxazine (2).

Embedded image Reaction formula 2 (wherein R ³ and X have the same meanings as described above)

The substituted phosphite dialkyl ester (3) is prepared by directly converting the corresponding aralkyl chloride or bromide and trialkyl phosphite or
It is obtained by heating in a solvent such as xylene.

On the other hand, in the general formula (1) of the present invention, n
= m = 0, Ar ¹ , Ar ² and R ¹ , R ² may be respectively the same or different, and 3,7-bisvinylphenothiazine and 3,7-bisvinylphenoxazine (1b) react with each other. Equation 3
Can be synthesized.

Embedded image Reaction formula 3 (wherein, Ar ¹ , R ¹ , Ar ² , R ² , R ³ and X have the same meaning as described above, and R ⁴ represents a lower alkyl group)

That is, 10-substituted 3,7-diformylphenothiazine or 10-substituted 3,7-diformylphenoxazine (2) and a 1-fold molar amount of a substituted dialkyl phosphite (3) are added in the presence of a base. Reaction, 10-substituted-3-vinyl-7
-Formylphenothiazine or 10-substituted-3-vinyl-7-formylphenoxazine (5) was synthesized and
By reacting with another phosphorous acid diethyl ester, the desired present compound (1b) can be synthesized.

5 is the case where R ¹ and R ² are not hydrogen atoms,
10-substituted-3-vinylphenothiazine or 10-substituted
-3- The compound can also be obtained by performing the usual Vielsmeyer-Haak reaction of vinylphenoxazine (6). (Reaction formula 4)

Embedded image Reaction formula 4 (wherein, Ar ¹ , R ¹ , R ³ and X have the same meanings as described above)

On the other hand, in the general formula (1) of the present invention, n
The phenothiazine derivative represented by = 0 and m = 1 and the phenoxazine derivative (1c) can be synthesized according to Reaction Scheme 5.

Embedded image Reaction formula 5 (wherein, Ar ¹ , R ¹ , Ar ² , R ² , and R ³ represent the same meaning as described above;
R ⁴ represents a lower alkyl group. That is, it can be obtained by reacting the monoformyl compound (5) synthesized by the above Reaction Scheme 3 or Reaction Scheme 4 with a diaryl 3-arylallyl phosphite (7).

The dialkyl 3-arylallyl phosphite (7) can be obtained according to the reaction formula 6.

Embedded image Reaction formula 6 (wherein Ar represents the above Ar ¹ or Ar ² , R represents the above R ¹ or R ² , Hal represents a halogen atom, and R ⁴ represents a lower alkyl group)

That is, (i) methylmagnesium chloride (MeMgCl) is reacted with the carbonyl derivative (8), and (i)
i) Then, the obtained alcohol compound is dehydrated in the presence of an acid to obtain an arylethylene (9). The acid is p-
What is usually used in a dehydration reaction such as toluenesulfonic acid (PTSA) can be used. Here, the arylethylene (9) is obtained by performing the same reaction as in the above (i) and (ii) except that the ketone derivative (10) is used as a starting compound and R-MgHal is used instead of methylmagnesium chloride. Can be.

Then, according to the method described in JP-A-49-75564, arylethylene (9) is reacted with paraformaldehyde (CH ₂ O) _n and hydrogen chloride in acetic acid to give 3-arylallyl chloride ( 11) get. Further, the 3-arylallyl chloride (11) and the trialkyl phosphite can be heated directly or in a solvent such as toluene or xylene to obtain the 3-alkylallyl phosphite dialkyl ester (7). Here, the alkyl group of the trialkyl phosphite includes a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group and an ethyl group are particularly preferable.

On the other hand, in the general formula (1) of the present invention, n
= m = 1, 3,7-bisbutadienylphenothiazine and 3,7-bisbutadienylphenoxazine (1d) in which Ar ¹ = Ar ² , R ¹ = R ² are synthesized according to Reaction Scheme 7. Can be. That is, 10-substituted 3,7-diformylphenothiazine and phenoxazine (2) were used in a two-fold molar amount thereof.
It can be produced by a method similar to the method of synthesizing 1a with 3-arylallyl dialkyl phosphite (7) in the presence of a base.

[0033]

Embedded image Reaction formula 7 (wherein, Ar ¹ , R ¹ , R ³ , and X have the same meanings as described above, and R ⁴ represents a lower alkyl group)

In the general formula (1) of the present invention, n
= m = 1, Ar ¹ , Ar ² and R ¹ , R ² may be the same or different, as appropriate, 3,7-bisbutadienylphenothiazine and 3,7-bisbutadienylphenoxazine ( 1
e) can be synthesized according to Reaction Scheme 8.

Embedded image Reaction formula 8 (wherein, Ar ¹ , R ¹ , Ar ² , R ² , R ³ and X have the same meaning as described above, and R ⁴ represents a lower alkyl group)

That is, the diformyl compound (2) and a one-fold molar amount
The diaryl 3-arylaryl phosphite (7) is reacted in the presence of a base to give 10-substituted-3-butadienyl-7-formylphenothiazine or 10-substituted-3-butadienyl-7-formylphenoxazine (12). The compound of the present invention (1) is synthesized and reacted with a dialkyl 3-arylallyl phosphite different from the above (7).
e) can be synthesized.

When the above-mentioned compound (1) of the present invention is used as a charge transporting material, a high carrier mobility can be obtained and a highly sensitive electrophotographic photosensitive member can be obtained. The compound (1) of the present invention can be used in a wide range of fields such as organic electroluminescence (EL). Specifically, the electrophotographic photoreceptor of the present invention comprises a compound (1) of the present invention as a charge transport material in a charge transport layer of a laminate type electrophotographic photosensitive member in which a charge generation layer and a charge transport layer are separated on a conductive support. ) Is used. Further, it can also be used as a charge transport material of a single-layer type electrophotographic photoreceptor containing the charge generation material and one or several kinds of charge transport materials in the same layer.

In the charge transport layer using the compound (1) of the present invention as a charge transporting material, only the compound (1) of the present invention can be directly deposited on a conductive support or a charge generating layer, or the compound (1) can be combined with the compound (1) of the present invention. It is formed by applying a solution in which a binder is dissolved in an appropriate solvent to a conductive support or a charge generation layer and drying the solution. On the other hand, a single-layer type photoreceptor containing a charge generating agent and the compound of the present invention (1) is prepared by dissolving or dispersing the charge generating agent and the compound of the present invention (1) in a suitable solvent together with a binder. It is obtained by coating on a support and drying. Further, a single-layer photoreceptor containing the compound (1) of the present invention and an electron acceptor type compound capable of forming a charge transfer complex with the compound (1) of the present invention can be obtained in the same manner.

As the binder, for example, polycarbonate, polyester, polystyrene, polyacrylate, polymethacrylate, polyamide, acrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin,
Examples thereof include polyurethane and copolymers thereof. In addition to such insulating polymers, organic photoconductive polymers such as polyvinyl carbazole, polyvinyl anthracene, and polyvinylene can be used.

Among these binders, polycarbonates represented by the general formula (F) are preferred. As specific examples, bisphenol A type polycarbonate represented by the formula (G) (for example, Iupilone E series manufactured by Mitsubishi Gas Chemical Co., Ltd.) and bisphenol Z type polycarbonate resin represented by the formula (H) (for example, Mitsubishi Polycarbonate Z series manufactured by Gas Chemical Co., Ltd.) is particularly preferred, and polycarbonates represented by formulas (I), (J) and (K) can also be used. These formulas (G) to
A copolymer comprising a mixture of monomer units represented by (K) can also be used. Among these, a copolymerized polycarbonate containing a biphenol carbonate unit represented by the formula (L) is preferable. As a specific example, a bisphenol A / biphenol type copolymerized polycarbonate resin represented by the formula (M) (here, n / n + m = 0.1 to 0.9 is desirable, and 0.7 to 0.9 is more desirable.

[0040]

Embedded image (F) (wherein, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹⁰ and R ¹¹ may be cyclically bonded. R ¹² , R ¹³ , R ^{14, R 15, R 16,} R
¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and n represents an integer of each of the above repeating units.

[0041]

Embedded image (G) (wherein, n represents an integer of the above repeating unit)

[0042]

Embedded image (H) (wherein, n represents an integer of the above repeating unit)

[0043]

Embedded image (I) (wherein, n represents an integer of the above repeating unit)

[0044]

Embedded image (J) (wherein, n represents an integer of each of the above repeating units)

[0045]

Embedded image (K) (wherein, n represents an integer of each of the above repeating units)

[0046]

Embedded image (L) (wherein, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ¹⁰ and R ¹¹ may be cyclically bonded. R ¹² , R ¹³ , and R ¹⁴ , R ¹⁵ , R ¹⁶ ,
^{R 17, R 18, R 19} , R 20, R 21, R 22, R 23, R 24, R
²⁵ , R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and m and n each represent an integer of each of the above repeating units.

[0047]

Embedded image (M) (wherein, n and m represent an integer of the above repeating unit. N /
n + m = 0.1-0.9)

In addition to the above-mentioned polycarbonates, polycarbonates having a repeating unit represented by the following structural formula and disclosed in JP-A-6-214412 can be used.

Embedded image (N) (wherein, n represents an integer of each of the above repeating units)

Further, a polycarbonate represented by the following structural formula disclosed in JP-A-6-222581 can also be used.

Embedded image (O) (wherein, R ²⁸ , R ²⁹ , and R ³⁰ may be the same or different;
A hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group, and n represents an integer of each of the above repeating units))

The mixing ratio of the binder and the compound (1) of the present invention is such that the charge transporting material is 10 to 1000 parts by weight, preferably 30 to 500 parts by weight, more preferably 100 to 100 parts by weight of the binder. 40 to 200 parts by weight can be added. The organic solvent used is not particularly limited, but includes alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl. Sulfoxides such as sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, esters such as ethyl acetate and methyl acetate, methylene chloride, chloroform, 1,2-dichloroethane, dichloroethylene, trichloroethylene, trichloroethane, carbon tetrachloride and the like Aliphatic halogenated hydrocarbons or aromatic compounds such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene may be used alone or in mixtures. Can.

As the conductive support used for the photoreceptor of the present invention, a sheet or drum made of foil or plate of a metal or alloy such as copper, aluminum, silver, iron, zinc, nickel or the like is used. Alternatively, these metals are vacuum-deposited or electrolytic-plated on a plastic film or cylinder, or a layer of a conductive compound such as a conductive polymer, indium oxide, or tin oxide is made of glass, paper or a plastic film, or the like. What is provided by coating or vapor deposition on a drum-shaped support is used.

The coating can be performed by using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a wire bar coating method, a blade coating method, a roller coating method, and a curtain coating method. Drying is preferably performed by drying at room temperature and then heating and drying. In general, the heating and drying is preferably performed at a temperature of 30 to 200 ° C. for 5 minutes to 2 hours in a still or blowing condition.

Further, the charge transport layer in the present invention may contain other charge transport materials and various additives as necessary. Other charge transfer materials include
For example, hydrazone compounds represented by the following general formula (I) described in JP-B-55-42380, JP-A-60-340999, JP-A-61-23154, etc .;
No. 3,873,312, etc., triphenylamine dimer represented by the following general formula (II) described in US Pat. Examples include, but are not limited to, system compounds, α-phenylstilbene, polyvinyl carbazole, triphenylmethane, and the like.

[0054]

Embedded image (I) (wherein, R ³¹ and R ³² may be the same or different and each may have a lower alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent R ³³ and R ³⁴ may be the same or different and may be a lower alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent A heterocyclic group which may have a substituent, wherein R ³³ and R ³⁴ may be bonded to each other to form a ring, and R ³⁵ may have a hydrogen atom, a lower alkyl group, or a substituent. A good aryl group, an aralkyl group which may have a substituent, a lower alkoxy group, or a halogen atom. R ³⁵ and R ³¹ or R ³² may be bonded to each other to form a ring)

[0055]

Embedded image (II) (wherein, R ^{36 to} R ⁴⁷ may be the same or different and each may be a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group substituted with a halogen atom, or an aryl optionally having a substituent. Represents a group or a halogen atom.)

[0056]

Embedded image (III) (wherein, R ^{48 to} R ⁵¹ may be the same or different and represent a lower alkyl group or an aryl group which may have a substituent;
⁴ , Ar ⁶ may be the same or different, a lower alkyl group,
It represents a phenylene group which may be substituted with one or more groups selected from a lower alkoxy group, an aryloxy group and a halogen atom. Ar ⁵ is a monocyclic or polycyclic aromatic ring having 4 to 14 carbon atoms which may have the same substituents as Ar ⁴ and Ar ⁶ , or has the same substituents as Ar ⁴ and Ar ⁶ Shows a good hetero ring. )

Various additives include, for example, those described in
Plasticizers such as biphenyl compounds, m-terphenyl, and dibutyl phthalate disclosed in 332206, surface lubricants such as silicone oils, graft-type silicone polymers, various fluorocarbons, potential stabilizers such as dicyanovinyl compounds and carbazole derivatives Agents, monophenolic antioxidants such as 2-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-methylphenol, bisphenol antioxidants, 4-diazabicyclo [2,
Examples thereof include amine antioxidants such as 2,2] octane, salicylic acid antioxidants, and tocopherol.

The thickness of the obtained charge transport layer is 5 to 40 μm, preferably 10 to 30 μm. The charge transport layer obtained as described above is electrically connected to the charge generation layer to receive the charge carriers injected from the charge generation layer in the presence of an electric field and to transfer these charge carriers to the photoconductor. It can have a function of transporting to the surface. In this case, the charge transport layer may be laminated on the charge generation layer, or may be laminated below the charge generation layer, but is preferably laminated on the charge generation layer.

A protective layer can be coated and formed on the photosensitive layer thus formed, if necessary. Further, an undercoat layer having a barrier function and an adhesive function can be provided between the conductive support and the photosensitive layer. Examples of a material for forming the undercoat layer include polyvinyl alcohol, nitrocellulose, casein, ethylene-acrylic acid copolymer, polyamide such as nylon, polyurethane, gelatin, and aluminum oxide. The thickness of the undercoat layer is 0.1 to
5 μm, preferably 0.5-3 μm, is suitable.

The charge generation layer may be made of an inorganic charge generation material such as selenium, selenium-tellurium, amorphous silicon, or a cation such as a pyrylium salt dye, a thiapyrylium salt dye, an azulenium salt dye, a thiacyanine dye, or a quinocyanine dye. Dyes, squarium salt pigments,
Polycyclic quinone pigments such as phthalocyanine pigments, anthantrone pigments, dibenzopyrene quinone pigments, pyranthrone pigments, indigo pigments, quinacridone pigments,
Azo pigments, using a material selected from organic charge generating substances such as pyrrolopyrrole pigments alone or in combination,
It can be used as a vapor deposition layer or a coating layer. Particularly preferably among the organic charge generating substances as described above,
Organic charge generating substances described in Chem. Rev. 1993, 93, p. 449-486.

Here, particularly as the phthalocyanine pigment, alkoxy titanium phthalocyanine (Ti (OR) ₂ Pc
), Oxo titanium phthalocyanine (TiOPc), copper phthalocyanine (CuPc), metal-free phthalocyanine (H ₂ Pc)
, Hydroxygallium phthalocyanine (HOGaPc), vanadyl phthalocyanine (VOPc), and chloroindium phthalocyanine (ClInPc). For more information, see Ti
OPc includes α-TiOPc, β-TiOPc, γ-TiOPc,
m-TiOPc, Y-TiOPc, A-TiOPc, B-TiOPc, Ti
OPc amorphous. As H ₂ Pc, α-H
₂ Pc, β-type H ₂ Pc, τ-type H ₂ Pc, and x-type H ₂ Pc.

These phthalocyanines can be used as a mixture by mixing and milling, or a mixture in which a new mixed crystal system is formed. For example, JP-A-4-371962, JP-A-5-2278, a mixed crystal of oxotitanyl phthalocyanine and vanadyl phthalocyanine described in JP-A-5-2279, and JP-A-6-148917, JP 6-14
Mixed crystals of oxotitanyl phthalocyanine and chloroindium phthalocyanine described in JP-A-5550, JP-A-6-271786, JP-A-5-297617 and the like can be used.

The azo compound is preferably a compound represented by the following structural formula.

Embedded image Bisazo (In the formula, R ⁵² represents a lower alkyl group.)

[0064]

Embedded image Trisazo

[0065]

Embedded image Cp ¹ of Cp ^1, Cp ² and trisazo bisazo, Cp ^2, Cp ³ (In the formula, R ⁵³ , R ⁵⁴ , R ⁵⁵ , and R ⁵⁶ may be the same or different and represent a hydrogen atom, a halogen group, or a lower alkyl group.) Further, a perylene compound represented by the following structural formula or Ring quinone compounds are also preferred.

[0066]

Embedded image (In the formula, R ⁵⁷ and R ⁵⁸ represent a hydrogen atom, a lower alkyl group, or an aryl group.)

[0067]

Embedded image

Other than these materials, any material can be used as long as it absorbs light and generates charges with high efficiency. As described above, an electrophotographic photosensitive member containing the phenothiazine derivative and the phenoxazine derivative (1) of the compound of the present invention in the charge transport layer can be obtained. As described above, the phenothiazine derivative and the phenoxazine derivative (1) of the compound of the present invention, that is, the compounds listed in Tables 1 to 4, are stable when formed into a film and have various properties when an electrophotographic photosensitive member is formed. It is a material with excellent characteristics.

[0069]

The present invention will be described below by way of examples.
The present invention is not limited to these. The measuring instruments and measuring conditions used in the examples are shown below. (1) ¹ H-NMR equipment: Brooker, AM-400 type apparatus (400 MHz) Solvent: CDCl ₃ or C ₆ D ₆ Internal standard substance: tetramethylsilane (2) MASS equipment: Hitachi M-80B (stock) Hitachi, Ltd.)

Example 1 3,7-bis (2 ', 2'-diphenylvinyl) -10-ethylphenothiazine (Exemplified compound 4, n = m = 0, X = S, Ar ¹ = R ¹ =
Synthesis of Ar ² = R ² = Ph, R ³ = ethyl group (1) 10-ethylphenothiazine (4a) 25 g of phenothiazine (0.
126 mol), 50.0 g (0.757 mol) of 85% KOH, 4.3 g (0.013 mol) of tetra-n-butylammonium hydrogen sulfate, 28.0 g (0.203 mol) of potassium carbonate, and 500 mL of toluene were weighed, and 39.0 g of ethyl iodide was added. g (0.250 mol) was added slowly. The reaction was performed at 60 to 70 ° C. for 5 hours, and the mixture was filtered. The filtrate was washed with water twice, dried over magnesium sulfate, and concentrated to obtain 28.7 g of a crude product. Ten
Recrystallized from 0 ml of isopropanol to give 23.99 g of
10-Ethylphenothiazine (4a) was obtained. 84.1% yield, mp 104-105 ° C

(2) 3,7-Diformyl-10-ethylphenothiazine (2a) 6.5 g (47.7 mmol) of dehydrated zinc chloride and toluene 15
0 ml of N, N-dimethylformamide (DM
F) 14 ml (180.1 mmol) and 10.0 g (44.0 mmol) of 10-ethylphenothiazine (4a) were added. From room temperature
At 35 ° C., 27.0 g (176.1 mmol) of phosphorus oxychloride was gradually added dropwise. After reacting at 73-78 ° C for 3 days, water 200m
l poured inside. After neutralization with sodium carbonate,
Stirred for hours. After liquid separation, the aqueous layer was extracted three times with ethyl acetate, and the collected organic layers were dried over magnesium sulfate and concentrated. Recrystallization from a mixed solvent consisting of isopropanol and ethyl acetate gave 4.96 g of 3,7-diformyl-10-ethylphenothiazine (2a). 58.7% yield, mp 132-145 ° C

[0072] ^{MS; 284 (M +),} 283, 268, 254, 236, 226, 198, 154. 1 H- NMR (CDCl 3) δ; 1.50 (t, J = 7.0Hz, 3H), 4.00
(q, J = 7.0Hz, 2H), 6.96 (d, J = 8.5Hz, 2H), 7.58 (s,
2H), 7.65 (d, J = 8.5Hz, 2H), 9.85 (s, 2H).

(3) Synthesis of 3,7-bis (2 ′, 2′-diphenylvinyl) -10-ethylphenothiazine (Exemplified Compound 4) 2.0 g of 3,7-diformyl-10-ethylphenothiazine (2a)
(7.1 mmol) and 4.7 g (15.5 mmol) of diethyl diphenylmethyl phosphite (3a) were dissolved in 20 ml of DMF, and 2.0 g (17.8 mmol) of potassium t-butoxide was dissolved.
Was gradually added. The mixture was allowed to react overnight at room temperature and then poured into 100 ml of methanol. The precipitate was taken out by filtration, dissolved in toluene, and purified by silica gel column chromatography (eluent; toluene / hexane = 1/1). Further, crystallization from ethyl acetate / ethanol gave 1.58 g of Exemplified Compound 4. Yield 38.3%, mp122-123 ° C

[0074] ^{MS; 583 (M +),} 554, 527, 292. 1 H- NMR (C 6 D 6) δ; 0.79 (t, J = 7.0Hz, 3H), 3.10
(q, J = 7.0Hz, 2H), 6.17 (d, J = 8.5Hz, 2H), 6.77 (d
d, J = 8.5Hz, J = 2.1Hz, 2H), 6.79 (s, 1H), 6.83 (d, J =
2.1Hz, 2H), 7.05-7.18 (m, 12H) ,, 7.20 (m, 4H), 7.3
2 (m, 4H).

Example 2 3,7-bis (4 ′, 4′-diphenylbutadienyl) -10-ethylphenothiazine (Exemplified compound 12, n = m = 1, X = S, Ar ¹
= R ¹ = Ar ² = R ² = Ph, R ³ = ethyl group) (1)
Synthesis of 1,1-diphenylethylene (9a) Magnesium 31.6 in a 2 liter reaction flask in a nitrogen stream
g (1.3 mol) and 50 ml of dry THF were charged, and a small amount of iodine and ethyl bromide were added. After confirming the start of the reaction, 600 ml of dry THF was added with stirring, and methyl chloride gas was blown therein. The blowing amount and cooling were controlled so as to keep the temperature at 30 to 40 ° C. The exotherm subsided in 2 hours and the magnesium disappeared. The blowing of methyl chloride gas was stopped, and the mixture was stirred at the same temperature for 1 hour to complete the preparation of Grineer. Next, 182.2 g (1.1 mol) of benzophenone (8a, Ar = R = Ph) and dry THF
365 ml of the mixture was added dropwise at 35 to 40 ° C. for 30 minutes, and the mixture was further stirred at the same temperature for 2 hours and further at the same temperature for 13 hours to complete the reaction. Under ice cooling, cooling 10% aqueous ammonium chloride solution 1.4 k
g, stirred for 30 minutes, allowed to stand, separated, washed with brine, dried over magnesium sulfate, concentrated, and crude carbinol
200.2 g (98.6% of theoretical yield from benzophenone) was obtained. Crude carbinol 200.2 in a 1 liter reaction flask
g, toluene 400ml, p-toluenesulfonic acid (PTS
A) 1 g was charged and toluene was refluxed (94 to 116).
° C) and azeotropic dehydration for 2 hours. After cooling, water washing, 2% soda ash water washing, water washing, drying with magnesium sulfate, concentration,
190.1 g of 1-diphenylethylene was obtained. This was distilled with Claisen with a vigreux to obtain 174.1 g of 1,1-diphenylethylene (9a, Ar = R = Ph). Bp103 ° C
/ 1 mmHg. 96.5% yield from benzophenone.

(2) Synthesis of 3,3-diphenylallyl chloride (11a, Ar = R = Ph) In a 300 ml reaction flask, 54.1 g (0.3 mol) of 1,1-diphenylethylene (9a), 108.26 g of acetic acid, Charge 13.5 g (0.45 mol) of formaldehyde and stir 30
13.67 g (0.375 mol) of hydrogen chloride was blown in at 3.5 ° C. for 3.5 hours. The reaction was cooled to keep the reaction temperature at 30 ° C. because it generated a weak heat. The injection of hydrogen chloride was stopped, and the mixture was stirred at the same temperature for 2 hours and then allowed to stand overnight. The reaction solution was poured into 200 ml of water, extracted with 200 ml of toluene, washed with water, washed with 2% soda ash, washed with water, dried over magnesium sulfate, and concentrated to obtain crude chloride 6
8.4 g were obtained. Distilled with Claisen with vigreux, 57.5
g was obtained. Bp120-132 ° C / 1mmHg. Yield 79%.

MS; 228 (M ⁺ ); 193,178,115 ¹ H-NMR (CDCl ₃ ) δ; 4.11 (2H, d, J = 8.0 Hz),
6.23 (1H, t, J = 8.0Hz), 7.21 ~ 7.41 (10H, m)

(3) Synthesis of 3,3-diphenylallyl phosphite diethyl ester (7a, Ar = R = Ph, R ⁴ = ethyl) 4,3 g-diphenylallyl chloride (11a) 40.8 g
(0.155 mol), 94.48 g of triethyl phosphite (0.
569 mol) was stirred under reflux for 24 hours. After confirming the disappearance of 3,3-diphenylallyl chloride (11a), the reaction was terminated. After cooling, distill with Claisen with Vigreux, 55.39 g
I got Bp 170-203 ° C / 1 mmHg. 99% of theoretical yield.

MS; 330 (M ⁺ ), 193,115 ¹ H-NMR (CDCl ₃ ) δ; 1.31 (6H, t, J = 7.0 Hz) 2.71 (2
H, dd, J = 7.9Hz, J = 22.4Hz), 4.08 (6H, dt, J = 7.1Hz, J = 7.6H
z), 6.12 (1H, q, J = 7.9Hz, J = 7.6Hz)), 7.22-7.38 (10H, m)

(4) 3,7-bis (4 ′, 4′-diphenylbutadienyl) -10-ethylphenothiazine (exemplary compound)
Synthesis of 12) 1.6 g (5.7 mmol) of 3,7-diformyl-10-ethylphenothiazine (2a), 4.1 g (12.4 mmol) of 3,7
3-diphenylallyl phosphite diethyl ester (7a)
It was dissolved in 20 ml of DMF, and 1.5 g (13.4 mmol) of potassium t-butoxide was gradually added at room temperature. The mixture was stirred overnight at the same temperature, and the mixture was poured into 50 ml of methanol. The precipitate was collected by filtration and purified by silica gel column chromatography (eluent; hexane / toluene = 1/1) to give 2.38 g of the desired product. Further recrystallization from a mixed solvent consisting of ethyl acetate and ethanol gave 1.47 g of Exemplified Compound 12. Yield 40.9%, mp183-184 ° C

[0081] ^{MS; 635 (M +);} 606, 191, 43. 1 H over _{NMR (C 6 D 6) δ} ; 0.90 (t, J = 7.0Hz, 3H), 3.
25 (q, J = 7.0Hz, 2H), 6.28 (d, J = 8.5Hz, 2H), 6.
51 (d, J = 15.4Hz, 2H), 6.89 (d, J = 11.1Hz, 2H),
6.92 (dd, J = 8.5Hz, J = 1.9Hz, 2H), 7.02 (d, J =
11.1Hz, 2H), 7.05-7.21 (m, 14H), 7.28 (m, 4H), 7.3
7 (m, 4H).

Example 3 3,7-bis (2 ′, 2′-diphenylvinyl) -10-p-tolylphenothiazine (Exemplified compound 22, n = m = 0, X = S, Ar ¹ =
R ¹ = Ar ² = R ² = Ph, R ³ = p-tolyl group) (1) 10-p-tolylphenothiazine (4b) phenothiazine 25 g (0.126 mol), p-iodotoluene
33 g (0.151 mol), 4 g (0.025 mol) of copper sulfate, 23 g of potassium carbonate and 200 ml of diisopropylbenzene
The reaction was carried out at 200 ° C for 3 hours at 200 ° C for 1 day. Cool the mixture,
After filtration through Celite, the filtrate was concentrated. The crystals were recrystallized from ethanol / ethyl acetate to give 27.5 g of 10-p-tolylphenothiazine (4b). 75.7% yield, mp 134 ° C

MS (direct); 289 (M ⁺ ), 273, 257, 24
^{1, 198, 166, 154. 1} H-NMR (CDCl 3) δ; 2.05 (s, 3H), 6.23 (d, J = 7.8Hz, 2
H), 6.57-6.68 (m, 4H), 6.95 (d, J = 7.3Hz, 2H), 6.92
(s, 4H).

(2) 3,7-Diformyl-10-p-tolylphenothiazine (2b) 10-p-tolylphenothiazine (4b) 20.0 g (69.1 mmol), zinc chloride 10.0 g (73.4 mmol), DMF22
ml (284.1 mmol) was stirred in 200 ml of toluene, and 27 ml (289.7 mmol) of phosphorus oxychloride was slowly added dropwise. The reaction was carried out at 80 ° C. for 3 days and poured into 300 ml of water. Neutralized with sodium carbonate and stirred at 80 ° C for 2 hours.
After liquid separation, the aqueous phase was extracted three times with toluene, and the collected organic phases were dried (MgSO ₄ ) and concentrated. The mixture was extracted from ethyl acetate with 2
The crystals were recrystallized twice to obtain 8.59 g of the desired product. 40.0% yield, mp215-217 ° C

[0085] MS (Direct); 345 (M +) ;, 316, 288. 1 H-NMR (CDCl 3) δ; 2.50 (s, 3H), 6.20 (d, J = 8.5Hz,
2H), 7.24 (d, J = 8.2Hz, 2H), 7.29 (dd, J = 8.6Hz, J = 1.
9Hz, 2H), 7.45 (d, J = 1.9Hz, 2H), 7.48 (d, J = 8.4Hz,
2H), 9.71 (s, 2H)

(3) 3,7-bis (2 ′, 2′-diphenylvinyl) -10-p-tolylphenothiazine (Exemplified Compound 2
Synthesis of 2) 3,7-Diformyl-10-p-tolylphenothiazine (2
b) 2.0 g (5.8 mmol) of diethyl diphenylmethyl phosphite (3a) 4.0 g (13.2 mmol) was added to DMF 20m2.
1 g of potassium t-butoxide in 1.5 g (13.4 g).
Mmol) was added slowly. Reaction overnight, methanol 10
The precipitated crystals were filtered off. The crystals were dissolved in chloroform, purified by silica gel column chromatography (toluene), and recrystallized from chloroform / hexane to give 1.48 g of the desired product. Yield 39.6%, mp265-268 ° C

[0087] MS (Direct); 645 (M +); 83. 1 H-NMR (CDCl 3) δ; 2.39 (s, 3H), 5.80 d, J = 6.2Hz, 2
H), 6.38 (d, J = 7.9Hz, 2H), 6.58 (brs, 2H), 6.73 (br
s, 2H), 7.11-7.18 (m, 6H), 7.21-7.36 (m, 18H)

Example 4 3,7-bis (4 ', 4'-diphenylbutadienyl) -10-p
-Tolylphenothiazine (Exemplified Compound 23, n = m = 1, X = S,
Synthesis of Ar ¹ = R ¹ = Ar ² = R ² = Ph, R ³ = p-tolyl group) 3,7-diformyl-10-p-tolylphenothiazine (2
b) 1.5 g (4.3 mmol) and 3.6 g (10.9 mmol) of diethyl 3,7-diphenylallylphosphite (7a) were added to DMF.
It was dissolved in 20 ml, and 1.3 g of potassium t-butoxide was gradually added. The reaction was carried out overnight, and 100 ml of methanol was added, and the precipitated crystals were separated by filtration. The crystals were purified by silica gel column chromatography (toluene / hexane = 1/1) and recrystallized from toluene / hexane to give 2.29 g of the desired product. 75.7% yield, mp247-249 ° C

MS (Direct); 697 (M ⁺ ); 493, 269, 16
^{9, 129. 1 H-NMR (} CDCl 3) δ; 2.10 (s, 3H), 5.97 (d, J = 8.6Hz,
2H), 6.42 (d, J = 15.2Hz, 2H), 6.61 (dd, J = 8.7Hz, J =
2.0Hz, 2H), 6.81 (d, J = 8.2Hz, 2H), 6.85 (d, J = 11.2H
z, 2H), 6.90-7.00 (m, 6H), 7.04-7.20 (m, 12H), 7.2
7 (m, 4H), 7.34 (m, 4H).

Example 5 3,7-bis (2 ', 2'-diphenylvinyl) -10-ethylphenoxazine (Exemplified compound 58, n = m = 0, X = O, Ar1 = R1 =
Synthesis of Ar2 = R2 = Ph, R3 = ethyl group) (1) 10-ethylphenoxazine (4c) Phenoxazine 3.0 g (16.4 mmol), 85% KOH 6.5 g
(98.5 mmol), potassium carbonate 3.7 g (26.8 mmol), tetra-n-butylammonium hydrogen sulfate 577 m
g (1.7 mmol) and 100 mL of toluene were weighed into a reaction flask, and 5.1 g (32.7 mmol) of ethyl iodide was added little by little from the dropping funnel (slightly exothermic).
Subsequently, the reaction was carried out at 60 to 80 ° C. for 7 hours. TLC
And gas chromatography confirmed disappearance of phenoxazine. After cooling, the toluene solution was washed three times with water. The toluene layer was dried (MgSO ₄ ), concentrated, and the residue was distilled under reduced pressure to give 2.
72 g of 10-ethylphenoxazine were obtained. Yield 78.7
%, Bp120-122 ° C / 1mmHg

[0091] ^{MS; 211 (M +);} 196, 182. 1 H- NMR (C 6 D 6) δ; 0.73 (t, J = 7.1Hz, 3H), 2.98
(q, J = 7.1Hz, 2H), 6.14 (d, J = 7.9Hz, 2H), 6.51 (d
t, J = 7.6Hz, 2H), 6.64 (t, J = 7.6Hz, 2H), 6.70 (d, J =
(7.7Hz, 2H).

(2) 3,7-Diformyl-10-ethylphenoxazine (2c) 2.7 g (12.8 mmol) of 10-ethylphenoxazine (4c), 3.8 g (52.0 mmol) of DMF, 1.8 g of zinc chloride
(13.2 mmol), 7.8 g (50.9 mmol) of phosphorus oxychloride and 50 ml of toluene were reacted in the same manner as in Example 1 (2).
Post-treatment gave 2.47 g of 3,7-diformyl-10-ethylphenoxazine (2c). 72.3% yield, mp199-200 ° C

MS; 267 (M ⁺ ); 252, 238, 224, 21
^{0, 182. 1 H- NMR (CDCl} 3) δ; 1.35 (t, J = 7.2Hz, 3H), 3.72
(q, J = 7.2Hz, 2H), 6.64 (d, J = 8.3Hz, 2H), 7.13 (d,
J = 1.8Hz, 2H), 7.37 (dd, J = 8.2Hz, J = 1.8Hz, 2H), 9.7
1 (s, 2H).

(3) Synthesis of 3,7-bis (2 ', 2'-diphenylvinyl) -10-ethylphenoxazine (Exemplified Compound 58) 3,7-Diformyl-10-ethylphenoxazine (2c) 1.
2 g (4.5 mmol), 3.5 g (11.5 mmol) of diethyl diphenylmethyl phosphite (3a) and 1.3 g of potassium t-butoxide were reacted in 20 ml of DMF in the same manner as in Example 1 (3), and poured into methanol. . The precipitate was purified by silica gel column chromatography (eluent; toluene / hexane = 1/1) and recrystallized from ethyl acetate to give 1.91 g of Exemplified Compound 58. 74.9% yield, mp216-217 ° C

[0095] ^{MS; 567 (M +);} 532, 283. 1 H- NMR (C 6 D 6) δ; 0.55 (t, J = 7.0Hz, 3H), 2.75
(q, J = 7.2Hz, 2H), 5.81 (d, J = 8.4Hz, 2H), 6.44 (d,
J = 2.0Hz, 2H), 6.52 (dd, J = 8.4Hz, J = 2.1Hz, 2H), 6.7
9 (s, 2H), 7.06-7.19 (m, 12H), 7.25 (m, 4H), 7.32
(m, 4H).

Example 6 3,7-bis (4 ', 4'-diphenylbutadienyl) -10-ethylphenoxazine (Exemplified compound 66, n = m = 1, X = O, Ar
Synthesis of ¹ = R ¹ = Ar ² = R ² = Ph, R ³ = ethyl group) 1.23 g of 3,7-diformyl-10-ethylphenoxazine (2c) (4.
3.4 mmol (10.3 mmol) of 3,3-diphenylallylphosphorous acid diethyl ester (7a), 20 ml of DMF
l, potassium-t-butoxide 1.5 g (13.4 mmol)
Was reacted and post-treated in the same manner as in Example 2 (4) to obtain 1.90 g of Exemplified Compound 66. Yield 66.5%, mp205-207 ° C

[0097] ^{MS; 619 (M +),} 590, 564. 1 H- NMR (C 6 D 6) δ; 0.69 (t, J = 7.0Hz, 3H), 2.86
(q, J = 7.1Hz, 2H), 6.53 (d, J = 15.3Hz, 2H), 6.67 (d
d, J = 8.4Hz, J = 1.9Hz, 2H), 6.73 (d, J = 1.9Hz, 2H), 6.
90 (d, J = 11.1Hz, 2H), 7.00-7.22 (m, 16H), 7.30 (m,
4H), 7.37 (m, 4H).

Synthesis Example 1 Synthesis of 2,7-bis (2 ′, 2′-diphenylvinyl) xanthene (Comparative Compound 1 Related to JP-A-6-271846) (1) Synthesis of 2,7-dibromoxanthene 5.0 g (27.4 mmol) of xanthene in chloroform 100
and 3.0 ml (58.2 mmol) of bromine was slowly added. Stirred at room temperature for 3 days and concentrated. The concentrate was recrystallized twice from chloroform to obtain 3.55 g of 2,7-dibromoxanthene. 38.1% yield, mp174-176 ° C

¹ H-NMR (CDCl ₃ ) δ; 3.99 (s, 2H), 6.91
(d, J = 9.1Hz, 2H), 7.26-7.31 (m, 4H). MS (direct); 340 (M ⁺ ); 259, 232, 180, 152, 1
26.

(2) Synthesis of 2,7-bis (2 ′, 2′-diphenylvinyl) xanthene 5.8 g (22.4 mmol) of 2,2-diphenyl-1-bromoethylene, 816 mg (33.6 mg equivalent) of magnesium,
A Grignard solution was prepared from 30 ml of THF. 3.0 g (8.8 mmol) of 2,7-dibromoxanthene, bis (1,3-
Diphenylphosphinopropane) nickel chloride (Ni
150 mg (0.28 mmol) of Cl ₂ DPPP and 10 ml of THF were suspended, and the above Grignard solution was added dropwise thereto. The mixture was refluxed for 3 days and poured into aqueous ammonium chloride. Celite filtration, toluene extraction, drying (MgSO ₄ ) and concentration, and the residue was subjected to silica gel column chromatography (eluent; toluene / hexane).
= 1/3) to give 650 mg of crude product. This was recrystallized twice from ethanol / methylene chloride to obtain 600 mg of the title compound. Yield 12.6%, mp173-174 ° C

¹ H-NMR (CDCl ₃ ) δ; 3.64 (s, 2H), 6.70-6.
81 (m, 6H), 6.89 (s, 2H), 7.18-7.22 (m, 4H), 7.24-7.3
7 (m, 16H). MS (direct); 538 (M ⁺ ); 359, 73, 45.

[0102]

Embedded image Comparative compound 1

Synthesis Example 2 Synthesis of 4,4′-bis (2 ″, 2 ″ -diphenylvinylphenyl) methylamine (Comparative Compound 2) 3.0 g of methyl-di- (p-formylphenyl) amine
(12.5 mmol), diethyl diphenylmethyl phosphite (3
a) 9.5 g (29.4 mmol), DMF 50 ml, potassium-
Example 1 3.4 g (30.3 mmol) of t-butoxide
Perform the same reaction and post-treatment as in (3) to obtain 5.05 g of comparative compound 2.
I got 74.9% yield, mp169-170 ° C

[0104]

Embedded image Comparative compound 2

Application Example 1 Oxotitanium phthalocyanine (TiOPc) was coated on an aluminum thin film deposited on a polyester film by 10 ^-6.
The charge generation layer was formed by vacuum evaporation to a thickness of about 0.8 μm at Torr. Further, 1 part of Exemplified Compound 4 and 1 part of a polycarbonate resin represented by the structural formula (H) (Mitsubishi Gas Chemical Co., Ltd., polycarbonate Z-200) were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied on the charge generation layer with a doctor blade, and dried at 80 ° C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were measured by a static method using an electrostatic recording tester EPA-8200 type (manufactured by Kawaguchi Electric Works). That is, the photoreceptor is charged by performing a corona discharge of -6 kV, the surface potential V0 (the unit is -V) is measured, and this is held for 5 seconds in a dark place (the surface potential Vi (the unit is -V)). Irradiate light with an illuminance of 5 lux from a halogen lamp, and apply a surface potential Vi
Necessary to reduce the intensity by half, that is, the half-reduction light amount E1 / 2
(Looks / second), the exposure amount E1 / 6 required to reduce the surface potential to 1/6, and the surface residual potential VR10 (−V) after irradiating with light of 5 lux for 10 seconds. The results are shown in Table 5.

Application Examples 2 and 3 In Application Example 1, instead of Exemplified Compound 4, Exemplified Compound
A photoreceptor was prepared in the same manner as in Examples 12 and 23, and the electrophotographic characteristics were evaluated. Table 5 shows the results.

Comparative Example 1 In Comparative Example 1, a comparative compound was used in place of Exemplified Compound 4.
A photoconductor was prepared in the same manner as in Example 1, except that Sample No. 1 was used, and the electrophotographic characteristics were evaluated. Table 5 shows the results. In addition, E1 / 2 and E1 / 6 could not be measured because no light attenuation was observed.

Comparative Example 2 A photoconductor was prepared in the same manner as in Application Example 1 except that Comparative Compound 2 was used instead of Exemplified Compound 4, and the electrophotographic characteristics were evaluated. Table 5 shows the results. E1 / 6 could not be measured. As is clear from Table 5, the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

Application Example 4 One part of chlordian blue (CDB) and one part of a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd. Iupilon E-2000) were kneaded in a ball mill for 5 hours using 30 parts of dichloroethane as a solvent. The obtained pigment dispersion is applied on a polyethylene terephthalate (PET) film by using a wire bar on a sheet on which aluminum is deposited, and dried at 45 ° C. for 3 hours to form a charge carrier generation layer to a thickness of about 1 μm. Had made. 1 part of Exemplified Compound 4 and a polycarbonate resin represented by the structural formula (H) (Mitsubishi Gas Chemical Co., Ltd. Polycarbonate Z)
One part was mixed and dissolved in 8 parts of dichloroethane. This liquid was applied on the charge carrier generating layer with a doctor blade,
For 3 hours to prepare a photoreceptor. The characteristics of the electrophotographic photosensitive member were evaluated in the same manner as in Application Example 1. The results are shown in Table 6.

Application Examples 5 and 6 In the application example 4, the exemplified compound is replaced with the exemplified compound 4
A photoreceptor was prepared in the same manner as in Examples 12 and 23, and the electrophotographic characteristics were evaluated. Table 6 shows the results.

Comparative Example 3 A photoconductor was prepared in the same manner as in Application Example 4, except that Comparative Compound 1 was used instead of Exemplified Compound 4, and the electrophotographic characteristics were evaluated. Table 6 shows the results. In addition, E1 / 2 and E1 / 6 could not be measured because no light attenuation was observed.

Comparative Example 4 A photoconductor was prepared in the same manner as in Application Example 4, except that Comparative Compound 2 was used instead of Exemplified Compound 4, and the electrophotographic characteristics were evaluated. Table 6 shows the results. E1 / 6 could not be measured. As is clear from Table 6, the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

Application Example 7 According to the method described in JP-A-1-291256, 35 parts of butyral resin (polyvinyl butyral BL-1 manufactured by Sekisui Chemical Co., Ltd.) was mixed with 35 parts of tetrahydrofuran 142.
To a binder resin solution obtained by dissolving in 5 parts, 40 parts of crystalline oxytitanyl phthalocyanine was added, and dispersed together with glass beads using a vibration mill for 2 hours. This dispersion was applied to a sheet obtained by evaporating aluminum on a polyethylene terephthalate (PET) film using a wire bar and dried to prepare a charge generation layer. Further exemplified compounds
1 part of 12 and 1 part of a polycarbonate resin represented by the structural formula (H) (Mitsubishi Gas Chemical Co., Ltd., polycarbonate Z) were mixed and dissolved in 8 parts of dichloroethane. This solution was applied on the charge generation layer with a doctor blade, and dried at 80 ° C. for 3 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. The results are shown in Table 7.

Application Example 8 In application example 7, the exemplified compound is replaced with the exemplified compound 12.
A photoreceptor was prepared in the same manner except that 23 was used, and the electrophotographic characteristics were evaluated. Table 7 shows the results.

Comparative Example 5 In the application example 7, a comparative compound was used in place of the exemplary compound 12.
A photoconductor was prepared in the same manner as in Example 1, except that Sample No. 1 was used, and the electrophotographic characteristics were evaluated. Table 7 shows the results. In addition, E1 / 2 and E1 / 6 could not be measured because no light attenuation was observed. As is clear from Table 7, the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

Application Example 9 One part of τ-type metal-free phthalocyanine (τ-H ₂ Pc) and butyral resin (polyvinyl butyral BL manufactured by Sekisui Chemical Co., Ltd.)
-1) One part was kneaded for 5 hours in a ball mill using 30 parts of tetrahydrofuran as a solvent. The obtained pigment dispersion was applied on a sheet in which aluminum was deposited on a polyethylene terephthalate (PET) film, and dried at 50 ° C. for 2 hours. Further, 1 part of Exemplified Compound 23 and 1 part of a polycarbonate resin represented by the structural formula (H) (Mitsubishi Gas Chemical Co., Ltd., Polycarbonate Z) were mixed and dissolved in 8 parts of dichloroethane. This liquid was applied on the charge generation layer with a doctor blade, and dried at 80 ° C. for 3 hours to prepare a photoreceptor.
The electrophotographic characteristics of this photoreceptor were measured in the same manner as in Application Example 1. The results are shown in Table 8.

Comparative Example 6 A photoconductor was prepared in the same manner as in Application Example 9 except that Comparative Compound 1 was used instead of Exemplified Compound 23, and the electrophotographic characteristics were evaluated. Table 8 shows the results. In addition, E1 / 2 and E1 / 6 could not be measured because no light attenuation was observed. As is clear from Table 8, the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

Application Example 10 1 part by weight of x-type metal-free phthalocyanine (x-H ₂ Pc) and 1 part by weight of butyral resin (Polyvinyl butyral BM-1 from Sekisui Chemical Co., Ltd.) were subjected to ball milling using 30 parts by weight of tetrahydrofuran as a solvent. Kneaded for 5 hours. The obtained pigment dispersion was applied on a sheet in which aluminum was deposited on a polyethylene terephthalate (PET) film and dried at 50 ° C. for 2 hours. Further, 1 part by weight of Exemplified Compound 12 and 1 part by weight of a polycarbonate resin represented by the structural formula (H) (Mitsubishi Gas Chemical Co., Ltd., Polycarbonate Z) were added to 1 part by weight of dichloroethane.
It was mixed and dissolved in 8 parts by weight. This solution was applied on the charge generation layer with a doctor blade, and dried at 80 ° C. for 2 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. The results are shown in Table 9.

Application Example 11 In the same manner as in Application Example 4, a charge generation layer using chlorodian blue was prepared. One part by weight of Exemplified Compound 4 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution is applied on the charge generation layer with a doctor blade and
After drying for an hour, a photoreceptor was prepared. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. Table 10 shows the results.

Application Example 12 In the same manner as in Application Example 4, a charge generation layer using chlorodian blue was prepared. One part by weight of Exemplified Compound 12 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution is applied on the charge generation layer with a doctor blade and
After drying for an hour, a photoreceptor was prepared. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. Table 10 shows the results.

Comparative Example 7 In the same manner as in Application Example 4, a charge generation layer using chlorodian blue was prepared. 1 part by weight of Comparative Compound 2 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution is applied on the charge generation layer with a doctor blade and
After drying for an hour, a photoreceptor was prepared. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. Table 10 shows the results. In addition, since sensitivity is insufficient, E
1/6 was not measurable. As is clear from Table 10,
It can be seen that the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

Application Example 13 In the same manner as in Application Example 7, a charge generation layer using crystalline titanyl phthalocyanine was produced. 1 part by weight of Exemplified Compound 4 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution was applied on the charge generation layer with a doctor blade and dried at 80 ° C. for 2 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. The results are shown in Table 11.

Application Example 14 In the same manner as in Application Example 7, a charge generation layer using crystalline titanyl phthalocyanine was produced. One part by weight of Exemplified Compound 12 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution was applied on the charge generation layer with a doctor blade and dried at 80 ° C. for 2 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. The results are shown in Table 11.

Comparative Example 8 In the same manner as in Application Example 7, a charge generation layer using crystalline titanyl phthalocyanine was produced. 1 part by weight of Comparative Compound 2 and 1 part by weight of a bisphenol A / biphenol type copolymerized polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd.) represented by the structural formula (M) were mixed and dissolved in 8 parts by weight of dichloroethane. This solution was applied on the charge generation layer with a doctor blade and dried at 80 ° C. for 2 hours to prepare a photoreceptor. The electrophotographic characteristics of the photoreceptor thus obtained were measured in the same manner as in Application Example 1. The results are shown in Table 11. E1 / 6 could not be measured due to insufficient sensitivity. As is clear from Table 11, the electrophotographic photoreceptor using the compound of the present invention has better sensitivity and a lower residual potential than the comparative compound.

[0125]

[Table 5]

[0126]

[Table 6]

[0127]

[Table 7]

[0128]

[Table 8]

[0129]

[Table 9]

[0130]

[Table 10]

[0131]

[Table 11]

[0132]

The electrophotographic photoreceptor using the charge transport material obtained by the present invention has excellent electrophotographic properties such as good solubility in a binder polymer, good sensitivity, and low residual potential. Which is extremely useful.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Toshimitsu Hagiwara 1-4-11 Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Takasago International Corporation

Claims (4)

[Claims] (1) The following general formula (1): (1) (wherein, Ar ¹ and Ar ² may be the same or different, each represents an aryl group which may have a substituent, and R ¹ ,
R ² , which may be the same or different, represents a hydrogen atom, a lower alkyl group, or an aryl group which may have a substituent. R ³ represents a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, an aryl group which may have a substituent, an aralkyl group which may have a substituent, X represents a sulfur atom or Represents an oxygen atom. n and m represent an integer of 0 or 1. And phenothiazine derivatives and phenoxazine derivatives. 2. A compound represented by the following general formula (1): (1) (In the formula, Ar ¹ and Ar ² may be the same or different, and may have a lower alkyl group, a lower alkoxy group, a halogen atom, a diarylamino group, and a dialkylamino group. Represents a group, and R ¹ and R ² may be the same or different, and each may be a hydrogen atom, a lower alkyl group, or a lower alkyl group, a lower alkoxy group, a halogen atom, a diarylamino group, a dialkylamino group. R ³ represents a lower alkyl group, an alicyclic hydrocarbon group having 5 to 7 carbon atoms, or a lower alkyl group, a lower alkoxy group, a halogen atom, a diarylamino group,
X represents an aryl group optionally having a dialkylamino group, or an aralkyl group optionally having a benzyl group, a tolylmethyl group, a methoxybenzyl group, or a chlorobenzyl group, and X represents a sulfur atom or an oxygen atom. n and m represent an integer of 0 or 1. A) phenothiazine derivative and phenoxazine derivative. 3. A charge transport material comprising the phenothiazine derivative and / or phenoxazine derivative according to claim 1. 4. An electrophotographic photosensitive member comprising the charge transport material according to claim 3.