JP4508710B2 - Electrophotographic photoreceptor - Google Patents

Description

The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor containing a phenanthrenediamine derivative having a predetermined sensitivity by having a specific substituent in the phenyl structure of a triphenylamino group at a molecular end.

Conventionally, as an electrophotographic photosensitive member for an image forming apparatus or the like, an organic photosensitive member made of an organic photosensitive material such as a charge transport agent (hole transport agent, electron transport agent), a charge generator, and a binder resin (binder resin). Is used. Such an organic photoreceptor is advantageous in that it is easy to manufacture and has a wide degree of freedom in structural design because it has various options for the photoreceptor material as compared with conventional inorganic photoreceptors.
Among such organophotoreceptor materials, phenanthrene diamine derivatives represented by the following general formula (40) are known as charge transporting agents having excellent initial sensitivity characteristics (see, for example, Patent Document 1). .

(In the general formula (40), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each represents a hydrogen atom, an alkyl group or a halogen atom. However, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ must not be hydrogen atoms at the same time.)

JP-A-6-21757 (Claims)

However, the phenanthrenediamine derivative described in Patent Document 1 has insufficient sensitivity characteristics due to low charge mobility, and also causes image defects due to exposure memory when used repeatedly for a long time. The problem was seen.
Therefore, the present inventors, by using a phenanthrenediamine derivative having a specific substituent at the molecular end, the charge mobility is increased, the sensitivity characteristics are excellent, and even when used repeatedly for a long time, The fact that no exposure memory is generated has been discovered, and the present invention has been completed.
That is, an object of the present invention is to use a phenanthrene amine derivative having a specific substituent at a molecular end that can be used suitably as a hole transport agent for an electrophotographic photosensitive member to solve the technical problems described above . It is an object of the present invention to provide an electrophotographic photoreceptor excellent in sensitivity characteristics and erasability of exposure memory.

According to the present invention, there is provided an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive gas, and the photosensitive layer has a phenanthrene rangeamine derivative represented by the following general formula (1) as a hole transport agent. An electrophotographic photosensitive member characterized by being contained is provided, and the above-mentioned problems can be solved.

(R < ¹ > -R < ⁸ > in General formula (1) is respectively independent, a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, and C1-C1 Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of ˜20 or a butyl group, or at least two of R ^{1 to} R ⁸ are each formed by bonding or condensation. , A carbocyclic structure .)

In constituting the electrophotographic photoreceptor of the present invention, the photosensitive layer is preferably a single layer type further containing a charge generating agent and an electron transporting agent.

In constituting the electrophotographic photoreceptor of the present invention, a plurality of R ^{1 to} R ⁴ in the general formula (1) are each an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an independent butyl group. It is preferable.

In constituting the electrophotographic photoreceptor of the present invention, a carbocyclic structure formed by condensation of R ¹ and R ² and R ³ and R ^{4 in} the general formula (1) is preferable.

In constituting the electrophotographic photosensitive member of the present invention, it is preferable that R ^{5 to} R ⁸ in the general formula (1) are each an independent hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In constituting the electrophotographic photoreceptor of the present invention, the phenanthrene diamine derivative represented by the general formula (1) is a method for producing a phenanthrene diamine derivative represented by the following reaction formula (1), Obtained by reacting the phenanthrenediamine derivative represented by the formula (2) with the halogenated benzene derivative represented by the general formulas (3) and (4) to perform a dehalogenation reaction. It is preferable to become.

(In the reaction formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of 20 or a butyl group, or at least two of R ^{1 to} R ⁸ are each formed by bonding or condensation, ( It is a carbocyclic structure , and X is a halogen atom.)

In constituting the electrophotographic photoreceptor of the present invention, the phenanthrenediamine derivative represented by the general formula (2) is represented by the general formula (5) as represented by the following reaction formula (2). A phenanthrenediamine derivative obtained by a reduction reaction after coupling the 9,10-phenanthrenequinone produced with the aniline derivative represented by the general formulas (6) and (7) Is preferred.

(In the reaction formula (2), R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of 20 or a butyl group, or two of R ⁷ and R ⁸ are carbocyclic structures formed by bonding or condensation. is there.)

In constituting the electrophotographic photoreceptor of the present invention, the halogenated benzene derivative represented by the general formula (3) is represented by the general formula (9) as represented by the following reaction formula (3). It is preferable to use a halogen derivative obtained by reacting a phosphoryl ylide derivative with a formylated benzene derivative represented by the general formula (10) by a Wittig method.

(In the reaction formula (3), R ¹ , R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, carbon An alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a butyl group, or at least two of R ¹ , R ^2, and R ⁵ are each bonded or (It is a carbocyclic structure formed by condensation, and X is a halogen atom.)

According to the present invention, since the photosensitive layer contains a phenanthrene diamine derivative having a predetermined structure represented by the general formula (1) as a hole transport agent, the charge mobility is excellent, so that the photosensitive layer is repeatedly used for a long time. Even when used, an electrophotographic photoreceptor excellent in sensitivity characteristics and exposure memory erasability can be obtained efficiently.
  That is, the phenanthrene diamine derivative represented by the general formula (1) has a specific substituent in the triphenylamine structure at the molecular end and has high charge mobility, so that it can be used repeatedly for a long time. Can provide an electrophotographic photoreceptor excellent in sensitivity characteristics and exposure memory erasability.

Further, according to the electrophotographic photosensitive member of the present invention, the photosensitive layer is a single layer type further containing a charge generating agent and an electron transporting agent, so that the sensitivity characteristics can be easily achieved despite the fact that the constitution and production are easy. In addition, it is possible to obtain a single layer type electrophotographic photoreceptor excellent in exposure memory erasability.

In addition, according to the electrophotographic photoreceptor of the present invention, when R ^{1 to} R ⁴ in the general formula (1) in the phenanthrenediamine derivative are predetermined aryl groups, the π-conjugated system is expanded, and charge transfer is performed. It has the feature that the degree is excellent. Therefore, an electrophotographic photosensitive member having excellent sensitivity characteristics can be provided.

Further , according to the electrophotographic photosensitive member of the present invention, it is a substituted or unsubstituted carbocyclic structure formed by condensation of R ¹ and R ² and R ³ and R ^{4 in} the general formula (1). Thus, the π-conjugated system spreads and the charge mobility is excellent. Therefore, an electrophotographic photosensitive member having excellent sensitivity characteristics can be provided.

In addition, according to the electrophotographic photosensitive member of the present invention, when R ^{5 to} R ⁸ in the general formula (1) are hydrogen atoms, it becomes easy to produce a stilbene derivative having a predetermined structure. It can be obtained stably.
Moreover, when R < ⁵ > -R < ⁸ > in General formula (1) is a predetermined | prescribed alkyl group, it has the characteristic that it is excellent in the solubility to binder resin. That is, when used as a hole transporting agent in an electrophotographic photoreceptor, it is uniformly dispersed in the photosensitive layer, so that the sensitivity characteristics are excellent over a long period of time, and the manufacture of the electrophotographic photoreceptor is facilitated. Therefore, it is possible to efficiently provide an electrophotographic photosensitive member having excellent sensitivity even when used repeatedly for a long time.

In addition, according to the electrophotographic photoreceptor of the present invention, a phenanthrene diamine derivative represented by the general formula (1) is obtained by reacting a predetermined phenanthrene diamine derivative with a predetermined halogenated benzene derivative. Can be obtained efficiently.

Moreover, according to the electrophotographic photoreceptor of the present invention, as a phenanthrenediamine derivative represented by the general formula (2), a predetermined reaction using a predetermined phenanthrenequinone derivative and a predetermined aniline derivative as raw materials. By using the obtained phenanthrene diamine derivative, a phenanthrene diamine derivative having such a predetermined structure can be efficiently obtained. As a result, the phenanthrene diamine derivative represented by the general formula (1) is more efficiently obtained. Can get to.

In addition, according to the electrophotographic photoreceptor of the present invention, the halogenated benzene derivative represented by the general formula (3) can be obtained by a predetermined reaction using a predetermined phosphorus ylide derivative and a predetermined formylated benzene derivative as raw materials. By using the halogenated benzene derivative, a halogenated benzene derivative having such a predetermined structure can be efficiently obtained, and as a result, the phenanthrenediamine derivative represented by the general formula (1) can be more efficiently obtained. it can.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments relating to a phenanthrenediamine derivative, a production method thereof, and an electrophotographic photoreceptor in the present invention will be specifically described with reference to the drawings as appropriate.

[First embodiment]
The first embodiment is a phenanthrene amine derivative represented by the following general formula (1) as a hole transport agent in the electrophotographic photoreceptor of the present invention . In addition, R < ¹ > -R < ⁸ > in General formula (1) is the definition already mentioned above.

  Here, the phenanthrene diamine derivative (HTM-A, B) represented by the following formulas (11) and (12) is shown as an example of the phenanthrene diamine derivative represented by the general formula (1).

Moreover, it is preferable that R < ¹ > -R < ⁴ > in General formula (1) is a C6-C30 aryl group substituted or unsubstituted by the respectively independent butyl group .
This is because the electron mobility is increased and the charge injection property from the charge generating agent can be improved by delocalizing and planarizing the electron distribution.
Therefore, an electrophotographic photosensitive member having excellent sensitivity characteristics can be provided by using it as a hole transport agent in the electrophotographic photosensitive member.
Moreover, if it is an aryl group, introduction | transduction is comparatively easy and the phenanthrene diamine derivative which has predetermined | prescribed stability can be obtained with a comparatively high yield.

Further, it is preferable to form a carbocyclic structure formed by condensation of R ¹ and R ² and R ³ and R ⁴ in the general formula (1).
This is because the electron mobility is increased and the charge injection property from the charge generating agent can be improved by delocalizing and planarizing the electron distribution.
Therefore, an electrophotographic photosensitive member having excellent sensitivity characteristics can be provided by using it as a hole transport agent in the electrophotographic photosensitive member.
Also, with such a structure, introduction is relatively easy, and a phenanthrenediamine derivative having a predetermined stability can be obtained in a relatively high yield.

Moreover, it is preferable that R < ⁵ > -R < ⁸ > in General formula (1) is a hydrogen atom or a predetermined alkyl group.
This is because, when R ^{5 to} R ⁸ in the general formula (1) are hydrogen atoms, the production of a stilbene derivative having a predetermined structure is facilitated, and such a derivative can be obtained stably. In addition, because R ^{5 to} R ⁸ in the general formula (1) are predetermined alkyl groups, it is possible to obtain a feature that the solubility in the binder resin is excellent.
Therefore, by using it as a hole transport agent in an electrophotographic photoreceptor, an electrophotographic photoreceptor excellent in sensitivity characteristics can be efficiently provided even when used repeatedly for a long time.

[Second Embodiment]
The second embodiment is a method for producing a phenanthrene diamine derivative as a hole transport agent in the electrophotographic photoreceptor of the present invention represented by the following reaction formula (1), which is represented by the general formula (2). The phenanthrene range represented by the general formula (1) is reacted with the halogenated benzene derivative represented by the general formulas (3) and (4) and dehalogenated. It is a method for producing a phenanthrenediamine derivative characterized in that an amine derivative is obtained.
In addition, R < ¹ > -R < ⁸ > and X in Reaction formula (1) are the contents already defined above.

1. Synthesis of Phenanthrene Range Amine Derivative First, in describing the reaction formula (1), a method for synthesizing the phenanthrene range amine derivative represented by the general formula (2) as a raw material will be described in detail.

(1) Reaction formula It is preferable to synthesize | combine the phenanthrene amine derivative represented by General formula (2) using a coupling reaction and a reduction reaction, as shown in the following reaction formula (2).
That is, after a phenanthrenequinone derivative represented by the general formula (5) and an aniline derivative represented by the general formulas (6) and (7) are subjected to a coupling reaction, the obtained general formula (8) It can obtain by carrying out the reductive reaction of the fence range amine derivative represented by these.
In addition, R ⁷ and R ⁸ in the reaction formula (2) are the same as the contents of the reaction formula (1), and have already been described above.

(2) Specific Reaction Step (2) -1 First Step In the first step, 9,10-phenanthrenequinone represented by the general formula (5) and the general formulas (6) and (7) It is preferable to synthesize a phenanthrenediamine derivative represented by the general formula (8) by reacting with the aniline derivative represented.

Here, the addition ratio of the 9,10-phenanthrenequinone represented by the general formula (5) and the two aniline derivatives (total amount) represented by the general formulas (6) and (7) is: The molar ratio is preferably in the range of 1: 1 to 1: 5.
The reason for this is that when the addition ratio of the phenanthrenequinone and the two types of iodobenzene derivatives is less than 1: 1, the production amount of the target phenanthrene derivative may be reduced. On the other hand, when the addition ratio of the phenanthrene diamine derivative and the two types of aniline derivatives exceeds 1: 5, a large amount of unreacted aniline derivative remains. This may be difficult.
In addition, it is preferable to make the addition ratio of the aniline derivative represented by the general formulas (6) and (7) a value of about 1: 1 in terms of molar ratio.

In addition, the reaction temperature is usually −20 to 50 ° C. in reacting the fence range amine derivative represented by the general formula (5) with the two types of aniline derivatives represented by the general formulas (6) and (7). The reaction time is preferably in the range of 1 to 12 hours.
This is because, under such reaction conditions, a desired reaction can be efficiently realized using a relatively simple manufacturing facility.

  Moreover, as a solvent used when synthesizing the phenanthrene amine derivative represented by the general formula (8), any solvent that does not affect the synthesis reaction may be used. For example, diethyl ether, tetrahydrofuran, dioxane, etc. Preferred examples include ethers; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; aromatic hydrocarbons such as benzene and toluene; dimethylformamide and the like.

Examples of the catalyst used for synthesizing the phenanthrenediamine derivative represented by the general formula (8) include organic sulfonic acids such as concentrated sulfuric acid and p-toluenesulfonic acid; polyphosphoric acid, titanium tetrachloride (TiCl ₄ ), Lewis acids such as zinc dichloride (ZnCl ₂ ), aluminum trichloride (AlCl ₃ ), tin tetrachloride (SnCl ₄ ), boron trifluoride (BF ₃ ); or polystyrene sulfonic acid, Nafion, etc. And a polymer carrier having sulfonic acid groups bonded thereto.
Here, it is preferable to make the addition amount of this catalyst into the value within the range of 1-5 mol with respect to 1 mol of phenanthrene diamine derivatives represented by General formula (5).
This is because when the amount of the catalyst added is less than 1 mol, the phenanthrenediamine derivative represented by the general formula (5) and the two types represented by the general formulas (6) and (7) are used. This is because the reactivity with the aniline derivative may be significantly reduced.
On the other hand, when the amount of the base added exceeds 5 mol, a phenanthrenediamine derivative represented by the general formula (5) and two aniline derivatives represented by the general formulas (6) and (7); This is because it may be extremely difficult to control the reaction between the two.

(2) -2 Second Step Next, a phenanthrene amine derivative represented by the general formula (8) is subjected to a reduction reaction to synthesize a fence range amine derivative represented by the general formula (2).

Examples of the reducing agent used in the synthesis of the phenanthrenediamine derivative represented by the general formula (2) include hydrogen (H ₂ ) / platinum (Pt) and hydrogen (H ₂ ) / palladium (Pd). , Hydrogen (H ₂ ) / Nickel (Ni), lithium aluminum hydride (LiAlH ₄ ), sodium borohydride (NaBH ₄ ), zinc (Zn), tin (Sn) and the like.
Here, it is preferable to make the addition amount of this reducing agent into the range of 1-10 mol with respect to 1 mol of phenanthrene amine derivatives represented by General formula (8). Furthermore, it is more preferable to set it in the range of 2-6 mol.

2. Synthesis of Halogenated Benzene Derivative Here, a method for synthesizing the halogen derivative represented by the general formula (3) used as a raw material when carrying out the reaction formula (1) is described in detail.

(1) Reaction Formula As shown in the following reaction formula (3), the halogenated benzene derivative represented by the general formula (3) is preferably synthesized using a Wittig reaction.
That is, the phosphorylylide derivative represented by the general formula (9) and the formylated benzene derivative represented by the general formula (10) are subjected to a Wittig reaction to form a halogenated benzene represented by the general formula (3). Derivatives can be obtained.
In the reaction formula (3), R ¹ , R ² , R ⁵ and X are the same as the contents of the reaction formula (1), and have already been described above.

(2) Reaction conditions Here, the addition ratio of the phosphorus ylide derivative represented by the general formula (9) and the formylated benzene derivative represented by the formula (10) is 1: 0.4 to 1: A value in the range of 1.5 is preferable.
This is because the unreacted phosphorus ylide derivative remains in a large amount when the addition ratio of the phosphorus ylide derivative and the formylated benzene derivative is less than 1: 0.4, and is represented by the general formula (3). This is because it becomes difficult to purify the halogen derivative. On the other hand, when the addition ratio of the phosphorus ylide derivative and the formylated benzene derivative exceeds 1: 1.5, a large amount of unreacted formylated benzene derivative remains. Therefore, the halogen derivative represented by the general formula (3) This is because purification may be difficult.
Therefore, the addition ratio of the phosphorylide derivative represented by the general formula (9) and the formylated benzene derivative represented by the formula (10) is a value within a range of 1: 0.6 to 1: 1 in terms of molar ratio. More preferably.

Moreover, when making the phosphorus ylide derivative represented by General formula (9) react with the formylated benzene derivative represented by Formula (10), reaction temperature shall be normally set to the value within the range of -30-20 degreeC. In addition, the reaction time is preferably set to a value within the range of 5 to 120 minutes.
This is because, under such reaction conditions, a desired reaction can be efficiently performed using a relatively simple manufacturing facility.
Examples of the reagent used in the Wittig method include sodium alkoxide such as n-butyllithium, sodium methoxide and sodium ethoxide; one kind of metal hydride such as sodium hydride and potassium hydride alone or A combination of two or more types can be mentioned.

Further, in carrying out the reaction formula (1), the synthesis method of the halogen derivative represented by the general formula (4) as a raw material is the same as the synthesis method of the halogen derivative represented by the general formula (3). Content. In the reaction formula (3), R ¹ , R ² , and R ⁵ are replaced with R ³ , R ⁴ , and R ⁶ . Further, the contents of R ³ , R ⁴ , and R ⁶ are the same as the contents of the reaction formula (1) and have already been described above.

3. Reaction conditions Here, the reaction conditions for carrying out the reaction formula (1) will be described in detail.
That is, it is preferable to synthesize the fanthrangeamine derivative represented by the general formula (1) using a dehalogenation reaction as shown in the above-described reaction formula (1).

(1) Reaction time and reaction temperature The reaction temperature between the phenanthrenediamine derivative represented by the general formula (2) and the two halogen derivatives represented by the general formulas (3) and (4) is usually from 80 to It is preferable to carry out at 300 degreeC, and it is preferable to make the reaction time into the value within the range of 1 to 24 hours.

(2) Solvent As a suitable solvent used in such a reaction, any solvent that does not affect the reaction may be used. For example, aromatic hydrocarbons such as toluene and xylene; nitrobenzene, dimethyl sulfoxide, N, Aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and HMPA are preferred.

(3) Base In addition, examples of a suitable base used in the reaction include inorganic bases such as potassium carbonate, lithium hydroxide, sodium hydroxide, and potassium hydroxide; or pyridine, picoline, triethylamine, N, N- Dimethylaniline, N-methylpyrrolidine, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,5-diazabicyclo [5.4.0] undecene-5 (DBU), 1,4- And organic bases such as diazabicyclo [2.2.0] octane (DBCO).

(4) Catalyst Moreover, as a suitable catalyst used for this reaction, copper powder, copper oxide, cuprous chloride, copper sulfate, copper acetate etc. are mentioned, for example.

(5) Addition ratio In carrying out the reaction between the phenanthrenediamine derivative represented by the general formula (2) and the two halogenated benzene derivatives represented by the general formulas (3) and (4) The ratio is preferably set to a value in the range of 1: 2 to 1: 5 in terms of molar ratio.
The reason for this is that when the addition ratio of the phenanthrene diamine derivative and the halogenated benzene derivative is less than 1: 2, the phenanthrene diamine derivative and the halogenated benzene derivative react in an appropriate manner. This is because it may be difficult to do. Moreover, when this addition ratio exceeds 1: 5, many unreacted halogen derivatives remain | survive and it may become difficult to refine | purify.
Therefore, the addition ratio of the phenanthrenequinone derivative represented by the general formula (2) and the halogen derivative represented by the general formulas (3) and (4) is 1: 2.5 to 1 in molar ratio. : A value within the range of 4 is preferable.

[Third Embodiment]
A third embodiment is an electrophotographic photosensitive member in which a photosensitive layer is provided on a conductive substrate, and the photosensitive layer contains a phenanthrene amine derivative represented by the general formula (1). An electrophotographic photoreceptor.
In addition, the electrophotographic photoreceptor includes a single layer type and a laminated type, and the electrophotographic photoreceptor having the phenanthrene diamine derivative of the present invention is applicable to both.
However, it can be used for both positive and negative charge types, has a simple structure and is easy to manufacture, can suppress film defects when forming a layer, has few interfaces between layers, and can improve optical characteristics, etc. From the viewpoint, it is preferably applied to a single layer type.
Since the electrophotographic photosensitive member having the phenanthrene diamine derivative of the present invention has excellent sensitivity characteristics, for example, as shown in FIG. 3 as an example of an image forming apparatus equipped with the electrophotographic photosensitive member. Is mentioned.

1. Single Layer Type Photoreceptor (1) Basic Configuration As shown in FIG. 1A, the single layer type photoreceptor 10 is obtained by providing a single photosensitive layer 14 on a conductive substrate 12.
For example, the photosensitive layer may be formed of a suitable phenanthrenediamine derivative (hole transport agent) represented by the general formula (1), a charge generator, a binder resin, and an electron transport agent as necessary. It can be formed by dissolving or dispersing in a solvent, coating the obtained coating solution on a conductive substrate and drying. Such a single layer type photoreceptor is characterized in that it can be applied to either a positive or negative charge type with a single configuration, has a simple layer configuration, and is excellent in productivity.
Further, since the obtained single layer type photoreceptor contains the phenanthrene diamine derivative represented by the general formula (1), it has excellent sensitivity characteristics and erasability of exposure memory. There is.
Further, when an electron transport agent is contained in the photosensitive layer of the single-layer type photoreceptor, electrons are efficiently exchanged between the charge generating agent and the hole transport agent, and the sensitivity and the like are more stable. There is a trend.

(2) Charge generator As the charge generator used in the present invention, for example, metal-free phthalocyanine, oxotitanyl phthalocyanine, perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, Examples thereof include one or a combination of two or more of squaraine pigment, trisazo pigment, indigo pigment, azurenium pigment, cyanine pigment and the like.
In particular, image forming apparatuses of digital optical systems such as laser beam printers and facsimiles using a light source such as a semiconductor laser require a photosensitive member having a sensitivity in a wavelength region of 700 nm or more. For example, metal-free phthalocyanine, A phthalocyanine pigment such as oxotitanyl phthalocyanine is preferably used.
On the other hand, an analog optical image forming apparatus such as an electrostatic copying machine using a white light source such as a halogen lamp requires a photosensitive member having sensitivity in the visible region. For example, a perylene pigment or a bisazo pigment is used. Etc. are preferably used.

(3) Hole transport agent In the electrophotographic photosensitive member of the present invention, it is also preferable to include other conventionally known hole transport agents in the photosensitive layer together with the phenanthrenediamine derivative which is a hole transport agent .
Examples of such a hole transport agent include various compounds having high hole transport ability, for example, compounds represented by the following general formulas (13) to (25) (HTM-1 to HTM-13).

Wherein R ^h1 , R ^h2 , R ^h3 , R ^h4 , R ^h5 and R ^h6 are independent of each other, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an alkoxy group. Represents a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a and b represent the same or different integers of 0 to 4, and c, d, e and f are the same or different. Represents an integer of 0 to 5. However, when a, b, c, d, e or f is 2 or more, each R ^h1 , R ^h2 , R ^h3 , R ^h4 , R ^h5 and R ^h6 are different. May be.)

(Wherein R ^h7 , R ^h8 , R ^h9 , R ^h10 and R ^h11 are independent of each other, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, a substituted or An unsubstituted aryl group having 6 to 40 carbon atoms, g, h, i and j are the same or different integers of 0 to 5 and k is an integer of 0 to 4. When g, h, i, j or k is 2 or more, each R ^h7 , R ^h8 , R ^h9 , R ^h10 and R ^h11 may be different.)

^{(Wherein, R h12, R h13, R} h14 and R ^h15 are independent of one another, a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl or alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted ^Represents an aryl group having 6 to 40 carbon atoms, and R ^h16 represents a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms. Represents an aryl group of 40. m, n, o and p represent the same or different integers of 0 to 5, and q represents an integer of 0 to 6. However, m, n, o, when p or q is 2 or more, each ^{R h12, R h13, R h14} , R h15 and R ^h16 may be different.)

( ^Wherein R ^h17 , R ^h18 , R ^h19 and R ^h20 are independent of each other, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted group, An aryl group having 6 to 40 carbon atoms, wherein r, s, t and u are the same or different and represent an integer of 0 to 5, provided that r, s, t or u is 2 or more. , Each R ^h17 , R ^h18 , R ^h19 and R ^h20 may be different.)

(In the formula, R ^h21 and R ^h22 are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group. R ^h23 , R ^h24 , R ^h25 and R ^h26 are independent of each other. And represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 40 carbon atoms.)

(In the formula, R ^h27 , R ^h28 and R ^h29 are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group.)

(In the formula, R ^h30 , R ^h31 , R ^h32 and R ^h33 are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group.)

(In the formula, R ^h34 , R ^h35 , R ^h36 , R ^h37 and R ^h38 are independent of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group.)

(In the formula, R ^h39 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ^h40 , R ^h41 and R ^h42 are independent of each other; a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms; Or an alkoxy group.)

(Wherein, R ^h43, R ^h44 and R ^h45 are independent of each other, represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 20 carbon atoms.)

(In the formula, R ^h46 and R ^h47 are independent of each other, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon atom having 6 to 6 carbon atoms. 40 aryl groups are shown.)

(In the formula, R ^h50 , R ^h51 , R ^h52 , R ^h53 , R ^h54 and R ^h55 are independent of each other, and are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an alkoxy group. Or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, α represents an integer of 1 to 10, and v, w, x, y, z and β may be the same or different. Represents an integer of 0 to 2, provided that when v, w, x, y, z or β is 2, each R ^h50 , R ^h51 , R ^h52 , R ^h53 , R ^h54 and R ^h55 may be different. .)

( ^Wherein R ^h56 , R ^h57 , R ^h58 and R ^h59 are independent of each other, and each ^represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group or alkoxy group having 1 to 20 carbon atoms, and Φ represents a formula (It is a group represented by any one of (26).)

  Further, in the present invention, together with the above-exemplified hole transport agents HTM-1 to HTM-13, etc., a conventionally known hole transport material, 2,5-di (4-methylaminophenyl) -1,3,4 Oxadiazole compounds such as oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, 1-phenyl-3- (p-dimethylamino) Pyrazoline compounds such as phenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds Nitrogen-containing cyclic compounds such as compounds, Singly or in combinations of two or more such engagement polycyclic compounds.

(4) Electron transport agent The electron transport agent used in the present invention is preferably a compound containing a quinone derivative. Examples thereof include diphenoquinone derivatives and naphthoquinone derivatives. The reason for this is that by using a specific compound as an electron transport agent, the electron acceptability is excellent and the compatibility with the charge generating agent is excellent. This is because a photographic photoreceptor can be provided.

  Specific examples of these electron transfer agents include compounds (ETM-A to ETM-C) represented by the following formulas (27) to (29).

Moreover, it is also preferable to use a conventionally known electron transport agent alone or in combination. Examples of such electron transporting agents include diphenoquinone derivatives, benzoquinone derivatives, anthraquinone derivatives, malononitrile derivatives, thiopyran derivatives, trinitrothioxanthone derivatives, 3,4,5,7-tetranitro-9-fluorenone derivatives, dinitroanthracene derivatives, Dinitroacridine derivatives, nitroantharaquinone derivatives, dinitroanthraquinone derivatives, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride And various compounds having an electron accepting property such as dibromomaleic anhydride, and one kind or a mixture of two or more kinds may be used.
Of these electron transfer agents, compounds having an electron mobility of 1.0 × 10 ⁻⁸ cm ² / V / sec or more at an electric field strength of 5 × 10 ⁵ v / cm are more preferable.

(5) Binder Resin Various resins conventionally used in the photosensitive layer can be used as the binder resin for dispersing each component. For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene Resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, polyamide resin, polyurethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin, ketone resin , Polyvinyl butyral resin, polyether resin, polyester resin, etc .; silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, other crosslinkable thermosetting resins; epoxy acrylate DOO, urethane - resin such as photocurable resin such as acrylate can be used.
In particular, a polycarbonate resin is a preferable binder resin because it is excellent not only in transparency and heat resistance but also in mechanical properties and compatibility with a hole transport agent.

(6) Additives In addition to the above-mentioned components, the photosensitive layer contains various conventionally known additives such as antioxidants, radical scavengers, singlet quenchers, and the like within a range that does not adversely affect the electrophotographic characteristics. Deterioration inhibitors such as char and ultraviolet absorbers, softeners, plasticizers, surface modifiers, extenders, thickeners, dispersion stabilizers, waxes, acceptors, donors, and the like can be blended. In order to improve the sensitivity of the photosensitive layer, a known sensitizer such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generator.

(7) Mixing ratio and thickness When the electrophotographic photosensitive member of the present invention is a single-layer type photosensitive member, the charge generating agent is 0.1 to 50 parts by weight, preferably 100 parts by weight of the binder resin. What is necessary is just to mix | blend in the ratio of 0.5-30 weight part. What is necessary is just to mix | blend the phenanthrene diamine derivative (hole transport agent) in this invention in the ratio of 20-500 weight part with respect to 100 weight part of binder resin, Preferably it is 30-200 weight part. When the electron transport agent is contained, the ratio of the electron transport agent is 5 to 100 parts by weight, preferably 10 to 80 parts by weight with respect to 100 parts by weight of the binder resin.

  In addition, when the electrophotographic photoreceptor of the present invention is a laminated photoreceptor, the charge generator and the binder resin constituting the charge generation layer can be used in various ratios, but the binder resin 100 can be used. It is appropriate to mix the charge generating agent in an amount of 5 to 1000 parts by weight, preferably 30 to 500 parts by weight with respect to parts by weight. In the case where a hole transport agent is contained in the charge generation layer, the ratio of the hole transport agent is 10 to 500 parts by weight, preferably 50 to 200 parts by weight with respect to 100 parts by weight of the binder resin. .

The hole transport agent constituting the charge transport layer and the binder resin can be used in various proportions within a range that does not inhibit charge transport and a range that does not crystallize. 10 to 500 parts by weight, preferably 25 to 200 parts by weight of the phenanthrene amine derivative (hole transport agent) in the present invention with respect to 100 parts by weight of the binder resin so that the charges can be easily transported. It is suitable to mix. When the charge transport layer contains an electron transport agent, the ratio of the electron transport agent is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the binder resin.

(8) Structure Further, the thickness of the photosensitive layer in the single-layer type photoreceptor is 5 to 100 μm, preferably 10 to 50 μm.
As the conductive substrate on which such a photosensitive layer is formed, various materials having conductivity can be used, for example, iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, Examples thereof include metals such as cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials on which the above metal is vapor-deposited or laminated, glass coated with aluminum iodide, tin oxide, indium oxide, and the like.

  Further, the shape of the conductive substrate may be any of a sheet shape, a drum shape, or the like in accordance with the structure of the image forming apparatus to be used. The substrate itself is conductive or the surface of the substrate is conductive. As long as it has. The conductive substrate preferably has sufficient mechanical strength when used. When the photosensitive layer is formed by a coating method, the charge generator, charge transport agent, binder resin, and the like exemplified above, together with a suitable solvent, a known method such as a roll mill, ball mill, attritor, paint shaker, super A dispersion liquid may be prepared by dispersing and mixing using a sonic disperser or the like, and this may be applied and dried by a known means.

  Further, regarding the configuration of the single-layer type photoreceptor, as shown in FIG. 1B, a barrier layer 16 is formed between the conductive substrate 12 and the photosensitive layer 14 in a range that does not impair the characteristics of the photoreceptor. The single-layer type photoreceptor 10 ′ may be used. Further, as shown in FIG. 1C, a single layer type photoreceptor 10 ″ having a protective layer 18 formed on the surface of the photosensitive layer 14 may be used.

(9) Production method Various organic solvents can be used as a solvent for preparing the dispersion. For example, alcohols such as methanol, ethanol, isopropanol and butanol; aliphatic systems such as n-hexane, octane and cyclohexane Hydrocarbons: aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate; dimethylformaldehyde, dimethylformamide, dimethylsulfo Sid and the like. These solvents are used alone or in admixture of two or more.
Further, a surfactant, a leveling agent or the like may be used in order to improve the dispersibility of the charge transport agent or charge generator and the smoothness of the photosensitive layer surface.

2. Multilayer Photoreceptor As shown in FIG. 2A, the multilayer photoreceptor 20 is formed by forming a charge generation layer 24 containing a charge generation agent on a conductive substrate 12 by means of vapor deposition or coating, Next, a coating solution containing at least one phenanthrene diamine derivative (hole transport agent) represented by the general formula (1) and a binder resin is applied onto the charge generation layer 24 and dried to charge. It is produced by forming the transport layer 22.
Contrary to the above structure, as shown in FIG. 2B, a multilayer photoreceptor 20 in which a charge transport layer 22 is formed on a conductive substrate 12 and a charge generation layer 24 is formed thereon. '
However, since the charge generation layer 24 is much thinner than the charge transport layer 22, for protection, the charge transport layer 22 is formed on the charge generation layer 24 as shown in FIG. It is more preferable to form
The charge generating agent, hole transporting agent, electron transporting agent, binder and the like can be the same as those of the single layer type photoreceptor.

In addition, a positive or negative charge type is selected depending on the formation order of the charge generation layer and the charge transport layer and the kind of the charge transport agent used in the charge transport 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 charge transport agent in the charge transport layer is the phenanthrene amine derivative in the present invention . When a positive hole transport agent is used, the photoconductor is negatively charged. In this case, the charge generation layer may contain an electron transport agent.
The multilayer electrophotographic photosensitive member of the present invention is characterized in that the residual potential of the photosensitive member is lowered and that it has a predetermined sensitivity.
The thickness of the photosensitive layer in the multilayer photoconductor is about 0.01 to 5 μm, preferably about 0.1 to 3 μm for the charge generation layer, and about 2 to 100 μm, preferably about 5 to 50 μm for the charge transport layer. It is.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

[Example 1]
(1) Synthesis of phenanthrene diamine derivative (HTM-A) (1) -1 Synthesis of phenanthrene diamine derivative Synthesis of a phenanthrene diamine derivative represented by the following formula (31) is carried out by the following reaction formula (4 ).
That is, in a two-necked flask having a volume of 2 l, 35 g (0.168 mol) of 9,10-phenanthrenequinone represented by the formula (5) and 62.7 g (0. 42 mol) and 300 ml of toluene were added and cooled to 0 ° C. Next, 79.7 g (0.42 mol) of titanium tetrachloride dissolved in 300 ml of toluene was added, the temperature was kept at 20 ° C., and the mixture was stirred for 3 hours. The obtained reaction liquid was dropped into a mixed liquid of 1000 ml of ion exchange water and 200 ml of toluene, and the produced toluene layer was washed with ion exchange water. Next, anhydrous sodium sulfate and activated clay were added to the organic layer containing toluene, followed by drying treatment and adsorption treatment. Thereafter, toluene was distilled off under reduced pressure, and the residue was further purified by silica gel column chromatography (developing solvent: chloroform solvent) to obtain 45.7 g of a phenanthrenediamine derivative represented by the formula (31) (yield: 58 .8%).

(1) -2 Synthesis of phenanthrene diamine derivative Subsequently, the phenanthrene diamine derivative represented by the formula (32) was synthesized according to the following reaction formula (5).
That is, 15 g (0.0319 mol) of phenanthrenediamine represented by the formula (31) and 100 ml of methanol (MeOH) were accommodated in a 500 ml flask and cooled to 0 ° C. Subsequently, 3.62 g (0.0956 mol) of sodium borohydride (NaBH ₄ ) was added, the temperature was maintained at 20 ° C., and the mixture was stirred for 3 hours. The obtained reaction solution was added dropwise to 400 ml of ion-exchanged water, and the precipitated solid product was filtered off. The obtained solid was dissolved with chloroform, and the organic layer was washed with ion-exchanged water three times. Thereafter, anhydrous sodium sulfate and activated clay were added to the obtained organic layer, followed by drying and adsorption treatment. Thereafter, chloroform was distilled off under reduced pressure, and the resulting residue was purified using silica gel column chromatography (developing solvent: chloroform solvent) to obtain 9.7 g of a phenanthrenediamine derivative represented by the formula (32) ( Yield 64%).

(1) -3 Synthesis of phosphorus ylide Subsequently, the synthesis of phosphorus ylide represented by the formula (34) was carried out according to the following reaction formula (6). That is, after adding 500 g (2.47 mol) of diphenylchloromethane and 492 g (3.00 mol) of triethyl phosphite, the mixture was heated with stirring at 160 ° C. for 3 hours. Then, after cooling to room temperature, excess triethyl phosphite was distilled off under reduced pressure to obtain 639 g of a phosphorus ylide derivative represented by the formula (34) (yield 85%).

(1) -4 Synthesis of Halogenated Benzene Derivative Next, a halogenated benzene derivative represented by the following formula (36) was carried out according to the following reaction formula (7). That is, after containing 20 g (0.0657 mol) of phosphorus ylide represented by the formula (34) in a two-necked flask having a volume of 500 ml kept at −20 ° C., argon gas replacement was carried out, and further 100 ml of dried THF And 41.1 ml (0.0657 mol) of n-BuLi hexane solution (concentration 1.6 mol / liter) were added and stirred for 10 minutes. Furthermore, 9.25 g (0.050 mol) of a formylated halogen derivative represented by the formula (35) was added, and the mixture was reacted at −20 ° C. with stirring for 15 minutes. The obtained reaction solution was poured into ion-exchanged water and extracted with toluene. Furthermore, the organic layer containing toluene was repeatedly washed with ion-exchanged water 5 times and then dried over anhydrous sodium sulfate. Thereafter, the solvent was distilled off, and the resulting residue was purified using silica gel column chromatography (developing solvent: chloroform solvent) to obtain 12.4 g of a triphenylamine derivative represented by the formula (36) (yield). Rate 74%).

(1) -5 Synthesis of phenanthrene diamine derivative Next, a phenanthrene diamine derivative represented by the following formula (11) was carried out according to the following reaction formula (8).
That is, 3.8 g (0.0275 mol) of anhydrous potassium carbonate and 0.175 g (0.00275 mol) of powdered copper were added into a 500 ml flask, heated for 2 hours, and stirred until uniform. Subsequently, 5.22 g (0.011 mol) of a phenanthrenediamine derivative represented by the following formula (32), 8.4 g (0.0251 mol) of a halogenated benzene derivative represented by the formula (36), After adding 50 ml of 2,4-trichlorobenzene, the mixture was reheated to 240 ° C. and reacted for 12 hours. Then, after cooling to room temperature, 50 ml of toluene was added and the filtration process was implemented. The obtained residue was dissolved in toluene and dried using activated clay. Thereafter, the obtained crystal was purified using silica gel column chromatography (developing solvent: chloroform solvent) to obtain 4.03 g of a phenanthrenediamine derivative represented by the formula (11) (yield 37.3%). )

(2) Production and Evaluation of Electrophotographic Photoreceptor A single-layer type electrophotographic photosensitive member using the phenanthrenediamine derivative (HTM-A) represented by the formula (11) obtained in Example 1 as a hole transporting agent. A body was prepared, and initial sensitivity (bright potential), sensitivity change after 1000 sheets of continuous printing, and image evaluation were measured. That is, 60 parts by weight of the obtained phenanthrenediamine derivative as a hole transporting agent and 5 parts by weight of an X-type metal-free phthalocyanine (CGM-A) represented by the following formula (37) as a charge generating agent Then, as a binder resin, 100 parts by weight of a polycarbonate resin (Resin-A) represented by the following formula (38) was added to 800 parts by weight of tetrahydrofuran as a solvent. Subsequently, it was mixed and dispersed for 50 hours using a ball mill to prepare a coating solution for a single-layer type photosensitive layer. The obtained coating solution is applied on a conductive substrate (aluminum base tube) by a dip coating method and dried with hot air at 100 ° C. for 30 minutes to form a single-layer type photosensitive layer having a thickness of 25 μm. An electrophotographic photosensitive member was obtained.
Next, the obtained electrophotographic photosensitive member was charged to 700 V using a drum sensitivity tester (manufactured by GENTEC), and then extracted from the light of the halogen lamp using a hand pulse filter with a wavelength of 780 nm. Monochromatic light (half-width: 20 nm, light quantity: 1.5 μJ / cm ² ) was exposed. The potential after the elapse of 330 msec after the exposure was measured and used as the initial sensitivity (V). Further, the obtained electrophotographic photosensitive member is mounted on a printer (Cryage 8331 modified machine manufactured by Kyocera Mita Co., Ltd.), charged to about 700 V, continuously printed 1000 sheets of A4 plain paper, and again Sensitivity was measured and used as post-running sensitivity. A value obtained by subtracting the initial sensitivity from the post-running sensitivity was calculated as the sensitivity change (V). The obtained results are shown in Table 1.

Further, after the obtained electrophotographic photosensitive member is mounted on the multi-function printer Antico 40 from which the charge eliminating lamp has been removed, the memory image evaluation document shown in FIG. 4 is continuously printed on 1000 sheets, and visually checked according to the following criteria. The image evaluation was carried out. The obtained results are shown in Table 1.
A: Generation of exposure memory in the gray area is not observed at all.
○: Almost no exposure memory is observed in the gray area.
Δ: Some exposure memory is observed in the gray area.
X: Remarkable generation of exposure memory is observed in the gray part.

[Example 2]
In Example 2, it represents with Formula (12) instead of the phenanthrene diamine derivative (HTM-A) represented with Formula (11) as a hole transport material in the coating liquid of Example 1. A single-layer photosensitive layer was prepared and evaluated in the same manner as in Example 1 except that the phenanthrene amine derivative was added.

[Comparative Example 1]
In Comparative Example 1, instead of the phenanthrene diamine derivative (HTM-A) used in Example 1, a phenanthrene diamine derivative (HTM-C) represented by the following formula (39) was used as a hole transport material. In the same manner as in Example 1, a single-layer type photosensitive layer was prepared and evaluated.

As described in detail above , the phenanthrenediamine derivative as a hole transport agent in the electrophotographic photoreceptor of the present invention has a high charge transport ability (holes) by having a specific substituent in the phenyl structure at the molecular end. Transportability). The electrophotographic photoreceptor of the present invention has excellent sensitivity characteristics and exposure memory erasability because the phenanthrenediamine derivative represented by the general formula (1) is used as a hole transport agent. Therefore, the electrophotographic photosensitive member of the present invention is expected to contribute to speeding up and high performance of various image forming apparatuses such as copying machines and printers.
Moreover, since the phenanthrene diamine derivative represented by the general formula (1) has a high hole transporting ability, it is suitably used as a hole transporting agent in an electrophotographic photoreceptor, solar cells, electroluminescence. It can be used in various fields such as devices.

(A)-(c) is a figure provided in order to demonstrate the basic structure and deformation | transformation structure of a single layer type photoreceptor. (A)-(b) is a figure provided in order to demonstrate the basic structure and deformation | transformation structure of a laminated type photoreceptor. FIG. 2 is a diagram for explaining an image forming apparatus including an electrophotographic photosensitive member. FIG. 5 is a diagram for explaining a memory image evaluation document.

10: Single layer type photoreceptor 12: Conductive substrate 14: Photoconductor layer 16: Barrier layer 18: Protective layer 20: Multilayer type photoreceptor 22: Charge transport layer 24: Charge generation layer 30: Copying machine 31: Image forming unit 31a: Image forming unit 31b: Paper feeding unit 32: Paper discharge unit 33: Image reading unit 33a: Light source 33b: Optical element 34: Document feeding unit 34a: Document loading tray 34b: Document feeding mechanism 34c: Document discharge tray 41: Photoconductor drum 42: Charger 43: Exposure source 44: Developer 45: Transfer roller 46: Cleaning device 50: Memory image evaluation document 51: White portion 52: Black portion 53: Gray portion

Claims (8)

An electrophotographic photoreceptor having a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer contains a phenanthrenediamine derivative represented by the following general formula (1) as a hole transporting agent. An electrophotographic photoreceptor.

(R < ¹ > -R < ⁸ > in General formula (1) is respectively independent, a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, and C1-C1 Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of ˜20 or a butyl group, or at least two of R ^{1 to} R ⁸ are each formed by bonding or condensation. , A carbocyclic structure .) 2. The electrophotographic photosensitive member according to claim 1 , wherein the photosensitive layer is a single layer type further containing a charge generating agent and an electron transporting agent. Formula (1) a plurality of R ¹ to R ⁴ in is in claim 1 or 2, characterized in that a substituted or unsubstituted aryl group having 6 to 30 carbon atoms in each independent butyl The electrophotographic photosensitive member described. The R ¹ and R ² and the R ³ and R ^{4 in the} general formula (1) are carbocyclic structures formed by condensation, according to any one of claims 1 to 3 . Electrophotographic photoreceptor . R < ⁵ > -R < ⁸ > in the said General formula (1) is an independent hydrogen atom or a C1-C20 alkyl group, respectively, The electron as described in any one of Claims 1-4 characterized by the above-mentioned. Photoconductor . The phenanthrene diamine derivative represented by the general formula (1) is a method for producing a phenanthrene diamine derivative represented by the following reaction formula (1), which is represented by the general formula (2): an amine derivative, with the general formula (3) and a halogenated benzene derivative represented by (4) is reacted, according to claim 1 to 5, characterized by being obtained by the process of performing dehalogenation The electrophotographic photosensitive member according to any one of the above.

(In the reaction formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of 20 or a butyl group, or at least two of R ^{1 to} R ⁸ are each formed by bonding or condensation, ( It is a carbocyclic structure , and X is a halogen atom.) As the phenanthrenediamine derivative represented by the general formula (2), as represented by the following reaction formula (2), 9,10-phenanthrenequinone represented by the general formula (5), 7. The electrophotographic photosensitive member according to claim 6 , wherein a phenanthrenediamine derivative obtained by a reduction reaction is used after a coupling reaction with the aniline derivative represented by the formulas (6) and (7). The body .

(In the reaction formula (2), R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. Or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkoxy group of 20 or a butyl group, or two of R ⁷ and R ⁸ are carbocyclic structures formed by bonding or condensation. is there.) As the halogen derivative represented by the general formula (3), as represented by the following reaction formula (3), a phosphorus ylide derivative represented by the general formula (9) and a formyl represented by the general formula (10) The electrophotographic photosensitive member according to claim 6 or 7 , wherein a halogenated benzene derivative obtained by reacting with a halogenated benzene derivative by a Wittig method is used.

(In the reaction formula (3), R ¹ , R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, carbon An alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a butyl group, or at least two of R ¹ , R ^2, and R ⁵ are each bonded or (It is a carbocyclic structure formed by condensation, and X is a halogen atom.)