JPH05148194A - Phenanthrene derivative and photoreceptor obtained by using the same compound - Google Patents

Abstract

PURPOSE:To provide new compounds showing a high sensitivity, excellent in charge-transferring properties, light-stability and durability and suitable, e.g. for an photoreceptor for electrophotography. CONSTITUTION:Compounds of formula I (R<1>-R<4> are an alkyl, an aryl or a heterocycle; R<5> and R<6> are H, a halogen, an alkyl or an aryl; (n) is 1-4), e.g. a compound of formula II. In addition, the compound of formula I can be obtained by reacting a compound of formula III with a compound of formula IV (R<7> is methyl, ethyl, etc.) in a solvent such as DHF.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenanthrene derivative suitable as a charge transporting material in a photoconductor used in an electrostatic copying machine, a laser beam printer or the like, and a photoconductor using the phenanthrene derivative.

[0002]

2. Description of the Related Art In recent years, organic photoconductors are widely used as photoconductors in image forming apparatuses such as copying machines because they are excellent in processability and economy and have a high degree of freedom in functional design. The Carlson process is widely used to form a copied image using a photoconductor. The Carlson process consists of a charging process that uniformly charges the photoconductor by corona discharge, an exposure process that exposes the document image on the charged photoconductor to form an electrostatic latent image corresponding to the document image, and an electrostatic latent image. After development with a developer containing toner, a developing step of forming a toner image, a transfer step of transferring the toner image to paper, a fixing step of fixing the transferred toner image, and a transfer step,
And a cleaning step for removing the toner remaining on the photoconductor. In order to form a high-quality image in the Carlson process, the photoconductor is required to have excellent charging properties and photosensitivity, and to have a low residual potential after exposure.

Conventionally, inorganic photoconductors such as selenium and cadmium sulfide have been known as photosensitive materials, but they have the drawbacks of toxicity and high production cost. Therefore, so-called organic photoconductors using various organic substances in place of these inorganic substances have been proposed. Such an organophotoreceptor has a photosensitive layer composed of a charge generating material that generates a charge upon exposure and a charge transporting material that has a function of transporting the generated charge.

In order to satisfy various conditions desired for such an organic photoreceptor, it is necessary to appropriately select these charge generating material and charge transporting material. Various organic compounds such as carbazole compounds, oxadiazole compounds, pyrazoline compounds, hydrazone compounds, stilbene compounds, and phenylenediamine compounds have been proposed as charge transport materials.

[0005]

However, all of the above-mentioned conventional charge-transporting materials have insufficient charge-transporting ability, poor light stability, or a binder resin constituting the photosensitive layer. There is a problem that it is poor in compatibility with and is crystallized with repeated use and is deposited from the photosensitive layer. Therefore, the photoreceptor using this charge transport material has a drawback that sensitivity and durability are not sufficient. It was

An object of the present invention is to provide a compound which is excellent in charge transporting ability and light stability and which is suitable as a charge transporting material, and a photoreceptor which uses the compound and which has high sensitivity and excellent durability. ..

[0007]

Means and Actions for Solving the Problems To solve the above problems, the phenanthrene derivative of the present invention has the general formula (I):

[0008]

[Chemical 2]

[Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and represent an alkyl group, an aryl group or a heterocyclic group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom or a halogen atom. , An alkyl group or an aryl group. n is 1
Indicates an integer of ˜4. ] Is represented. The photoreceptor of the present invention for achieving the above object is characterized in that a photosensitive layer containing a phenanthrene derivative represented by the general formula (I) is provided on a conductive substrate.

Since the phenanthrene derivative represented by the above general formula (I) has a structure of phenanthrene known as a quencher introduced into the molecule, it exhibits a high charge transporting ability and is excellent in photostability. .. Therefore, the photosensitive layer containing the phenanthrene derivative as a charge transport material has high sensitivity and excellent durability.

As described above, the reason why the phenanthrene derivative represented by the general formula (I) has high sensitivity and photostability is that the double bond of the phenanthrene moiety and the group bonded to the phenanthrene moiety or nitrogen atom Formed by
This is because the electron-conjugated system has a larger spread than that in the conventional charge transport material, so that the planarization of the molecular structure of the compound is further promoted and the intermolecular interaction due to the overlap between molecules is strengthened. Presumed.

Examples of the alkyl group include lower alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group. Be done. Examples of the aryl group include a phenyl group, an o-terphenyl group,
Examples thereof include naphthyl group, anthryl group and phenanthryl group.

Examples of the heterocyclic group include thienyl group, pyrrolyl group, pyrrolidinyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, 2H-imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyranyl group. , Pyridyl group, piperidyl group, piperidino group, 3-morpholinyl group, morpholino group and thiazolyl group. Also,
It may be a heterocyclic group condensed with an aromatic ring.

Specific examples of the phenanthrene derivative represented by the above general formula (I) include the following compounds.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

The phenanthrene derivative of the present invention can be synthesized by various methods, for example, the method shown in the following reaction formula.

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[In the formula, R ^{1 to} R ⁶ and n are the same as defined above. R ⁷ represents 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 preferably used. That is, as shown in the above reaction formula, the 9-bromo-10-formylphenanthrene derivative represented by the formula (a) is
The sodium amide represented by the formula (b) is reacted in the presence of a solvent to obtain an aldehyde compound represented by the formula (c). Then, the compound (c) is reacted with a methylphosphonate represented by the formula (d) in the presence of a basic substance and a solvent to form the phenanthrene derivative of the present invention represented by the formula (I). Is obtained.

The sodium amide represented by the formula (b) has the formula:
The methylphosphonate represented by the formula (d), which is used in an equimolar amount with respect to the 9-bromo-10-formylphenanthrene derivative represented by the (a), is an aldehyde compound represented by the formula (c). Used in equimolar amounts to. Examples of the basic substance include alcoholates such as sodium methylate, sodium ethylate, and potassium t-butyrate, as well as sodium acetate, sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride, and the like. Is 0.5 equivalent to the aldehyde compound represented by the formula (c).

The former, 9-bromo-10 represented by (a)
Examples of the solvent used in the reaction between the -formylphenanthrene derivative and the sodium amide represented by the formula (b) include benzene, N, N'-dimethylformamide and dimethyl sulfoxide. As the solvent used in the latter reaction of the aldehyde compound represented by the formula (c) and the methylphosphonate represented by the formula (d), methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve are used. And alcohols such as ethylene glycol and propylene glycol, ethers such as dioxane and tetrahydrofuran, N, N'-dimethylformamide, dimethylsulfoxide and the like. Among them, N, N'-dimethylformamide is preferable. used.

The amount of the solvent used is not particularly limited in any case, and it is sufficient if it is 1 to 20 times by weight the total amount of the compounds used in the reaction. The reaction temperature of the former reaction is 50-
It is preferably in the range of 80 ° C. On the other hand, the latter reaction sufficiently proceeds at room temperature without heating, but the reaction time may be shortened by heating. The reaction temperature is 10 to
It is preferably in the range of 110 ° C, preferably 20 to 70 ° C.
Is more preferably within the range.

The degree of progress of the reaction can be known by analyzing the reaction solution by thin layer chromatography, high performance liquid chromatography or the like. After completion of the reaction, the target product can be taken out by a usual method such as filtration or solvent extraction, and if necessary, it can be purified by a method such as recrystallization or column chromatography.

Incidentally, 9-bromo-10 represented by the formula (a)
-Formylphenanthrene derivatives are, for example, 9,10
-A dibromophenanthrene derivative in the presence of a solvent,
A 9-bromo-10-methylphenanthrene derivative was obtained by reacting with 0.5-fold molar amount of methyl iodide.
By reacting a bromo-10-methylphenanthrene derivative with potassium dichromate in the presence of a solvent,
It can be easily manufactured. As the solvent used in these reactions, benzene, toluene, xylene and the like are preferably used, and the reaction temperature is preferably in the range of 50 to 80 ° C.

The photoreceptor of the present invention is provided with a photosensitive layer containing one or more phenanthrene derivatives represented by the general formula (I) as a charge transport material. The photosensitive layer includes a so-called single layer type and a laminated type, but the present invention is applicable to both of them. In order to obtain a single-layer type photoreceptor, a photosensitive layer containing a compound represented by the general formula (I), which is a charge transport material, a charge generating material, a binder resin, etc., is applied by means such as coating. It may be formed on the conductive substrate.

Further, in order to obtain a laminated type photoreceptor, a charge generating layer containing a charge generating material is formed on a conductive substrate by means such as vapor deposition or coating, and on this charge generating layer,
A charge transport layer containing the compound represented by the general formula (I) and a binder resin may be formed. Also, contrary to the above,
The charge transport layer may be formed on the conductive substrate, and then the charge generation layer may be formed. Further, in the above-mentioned laminated type photosensitive layer, the charge generating layer may also contain a charge transport material.

As the charge generating material, conventionally used selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, azo compounds, disazo compounds, phthalocyanine compounds, anthanthrone compounds, perylene compounds. Examples thereof include compounds, indigo compounds, triphenylmethane compounds, slene compounds, toluidine compounds, pyrazoline compounds, perylene compounds, quinacridone compounds, and pyrrolopyrrole compounds. These charge generation materials can be used alone or in combination of two or more so that they have an absorption wavelength region in a desired region.

The phenanthrene derivative represented by the general formula (I), which is a charge transport material, can be used alone or in combination with other conventionally known charge transport materials. As the conventionally known charge transport material, various electron-withdrawing compounds and electron-donating compounds can be used. Examples of the electron-withdrawing compound include diphenoquinone derivatives such as 2,6-dimethyl-2 ', 6'-ditert-dibutyldiphenoquinone, malononitrile, thiopyran compounds, tetracyanoethylene, 2,4,8-triene. Examples include nitrothioxanthone, 3,4,5,7-tetranitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, and dibromomaleic anhydride.

As the electron-donating compound, 2,5
-Oxadiazole compounds such as di (4-methylaminophenyl) and 1,3,4-oxadiazole, 9- (4
-Styryl compounds such as diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole compounds Examples thereof include nitrogen-containing cyclic compounds such as compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, and triazole compounds, and condensed polycyclic compounds.

These charge transport materials may be used alone or in combination of two or more. When a charge transporting material having film-forming property such as polyvinylcarbazole is used,
The binder resin is not always necessary. As a binder resin,
Various resins can be used. For example, styrene-based polymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer , Chlorinated polyethylene, polyvinyl chloride, polypropylene,
Thermoplastic resin such as vinyl chloride-vinyl acetate copolymer, polyester, alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy Examples thereof include resins, phenol resins, urea resins, melamine resins, other crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins may be used alone or in combination of two or more.

The organic photosensitive layers of single-layer type and laminated type include
A sensitizer, a fluorene compound, an antioxidant, a deterioration inhibitor such as an ultraviolet absorber, and an additive such as a plasticizer may be contained. Further, in order to improve the sensitivity of the charge generation layer, known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generation material.

In the multi-layer type photoreceptor, the charge generating material and the binder resin which constitute the charge generating layer can be used in various proportions, but the binder resin can be used in an amount of 100 parts (weight part, hereinafter the same). 5 to 500 parts, especially 10 to 10 parts of the charge generating material.
It is preferably used in a ratio of 300 parts. The charge generation layer may have an appropriate film thickness, but 0.01 to 5
It is preferably formed to a thickness of 0.1 μm, particularly 0.1 to 3 μm.

The phenanthrene derivative (charge-transporting material) represented by the general formula (I) constituting the charge-transporting layer and the binder resin may be mixed in various amounts within a range that does not inhibit charge transport and a range that does not crystallize. Can be used in proportions,
In order to easily transport the charge generated in the charge generation layer by light irradiation, 100 parts of the binder resin may be added to the above general formula (I).
It is preferable to use the phenanthrene derivative represented by the formula in an amount of 10 to 500 parts, particularly 25 to 200 parts. Also,
The thickness of the laminated photosensitive layer is 0.01 to 5 μm for the charge generation layer.
The thickness of the charge transport layer is preferably 2 to 100 μm, particularly 5 to 50 μm.
It is preferable that the thickness is about m.

In the single-layer type photoreceptor, the binder resin 10
The charge generating material is 0.1 to 50 parts relative to 0 parts, and more preferably 0.1.
5 to 30 parts, 40 to 200 parts, especially 50 to 50 parts by weight of the phenanthrene derivative (charge transport material) represented by the general formula (I).
Suitably 100 parts. The thickness of the single-layer type photosensitive layer is preferably 5 to 100 μm, particularly preferably 10 to 50 μm.

In the case of a single-layer type photoreceptor, it is between the conductive substrate and the photosensitive layer, and in the case of the laminated type photoreceptor, it is between the conductive substrate and the charge generating layer, and the conductive substrate. A barrier layer may be formed between the charge transport layer and the charge transport layer or between the charge generation layer and the charge transport layer to the extent that the characteristics of the photoreceptor are not impaired. It may be formed.

As the conductive substrate on which the above layers are formed, various conductive materials can be used.
For example, simple metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, and iodide Examples thereof include glass coated with aluminum, tin oxide, indium oxide, or the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, the conductive substrate is preferably one having sufficient mechanical strength when used. When each of the above layers is formed by a coating method, the charge generation material, charge transport material, and
A binder resin and the like are mixed with a suitable solvent by a known method, for example, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser to prepare a coating solution, which is prepared by a known means. It may be applied and dried.

As the solvent for forming the coating solution, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol,
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran, Examples thereof include ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide and dimethyl sulfoxide. These solvents may be used alone or in combination 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 transporting material or the charge generating material, the dyeing property and the like. As described above, the charge generation layer may be formed by depositing the charge generation material.

[0043]

The present invention will be described in detail below with reference to examples and comparative examples. Example 1 <Synthesis of Phenanthrene Derivative Represented by Formula (1)> 2.85 g of 9-bromo-10-formylphenanthrene in which R ⁵ and R ⁶ in the formula (a) are both hydrogen atoms, and 1.91 g of sodium amide in which R ¹ and R ² in the formula (b) are both phenyl groups are added to potassium dichromate 2.0
An aldehyde compound in which 100 g of benzene and 3 g are dissolved in 100 ml of benzene and refluxed at 60 ° C. for 5 hours, and R ¹ and R ² in the formula (c) are both phenyl groups and R ⁵ and R ⁶ are both hydrogen atoms. 2.73 g (yield 73%) was obtained.

Then, the aldehyde compound 1.87
g is a phenyl group represented by R ³ and R ⁴ in the above formula (d),
Methylphosphonate ester 1.38 in which ⁷ is a methyl group
g, 0.41 g of sodium acetate, benzene 10
It was dissolved in 0 ml and refluxed at 60 ° C. for 5 hours to obtain the above formula (1).
2.00 g of the phenanthrene derivative represented by
%) Was obtained.

The analysis results of the obtained phenanthrene derivative are shown below. Elemental analysis result Calculated value (%) as C ₄₀ H ₂₉ N ₁ (= 523.68): C 91.74 H: 5.58
N: 2.67 Found (%): C: 91.73 H: 5.64
N: 2.65 Example 2 <Synthesis of Phenanthrene Derivative Represented by Formula (2)> Instead of the sodium amide used in Example 1, the above formula was used.
In the same manner as in Example 1 except that 1.29 g of sodium amide in which R ^{1 in} (b) was a phenyl group and R ² was a methyl group was used, R ¹ in the formula (c) was phenyl. Base,
2.46 g (yield 79%) of an aldehyde compound in which R ² is a methyl group and R ⁵ and R ⁶ are both hydrogen atoms was obtained.

Then, this aldehyde compound 1.56
g is reacted with 1.07 g of a methylphosphonic acid ester in which R ³ and R ⁴ in the formula (d) are both ethyl groups in the same manner as in Example 1 above, and is represented by the formula (2). 1.28 g (yield 70%) of the phenanthrene derivative was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis results C ₂₇ H ₂₇ N ₁ (= 365.52) Calculated value (%): C: 88.72 H: 7.45
N: 3.83 actual value (%): C: 88.65 H: 7.42
N: 3.79 Example 3 <Synthesis of Phenanthrene Derivative Represented by Formula (3)> Instead of the sodium amide used in Example 1, the above formula was used.
R ¹ in (b) in, except that R ² is using sodium amide 0.95g ethyl Both, in the same manner as in Example 1, R ¹ in the formula (c), R ² are both Ethyl group, R
Aldehyde compounds in which both ⁵ and R ⁶ are hydrogen atoms 2.
11 g (yield 76%) was obtained.

Next, this aldehyde compound 1.39
g is reacted with 0.90 g of a methylphosphonate in which R ³ and R ⁴ in the formula (d) are both phenyl groups in the same manner as in Example 1 above, and is represented by the formula (3) 1.69 g (yield 79%) of the phenanthrene derivative was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis result Calculated value (%) as C ₃₂ H ₂₉ N ₁ (= 427.59): C: 89.89 H: 6.84
N: 3.28 Found (%): C: 89.87 H: 6.87
N: 3.37 Example 4 <Synthesis of Phenanthrene Derivative Represented by Formula (4)> Instead of the sodium amide used in Example 1, the above formula was used.
(b) R ¹ is a phenyl group in, except for using sodium amide 2.41 g R ² is β- naphthyl group, in the same manner as in Example 1, R ¹ in the formula (c) Is a phenyl group, R ² is a β-naphthyl group, and R ⁵ and R ⁶ are both hydrogen atoms. 3.47 g of an aldehyde compound (yield 82%)
Got

Next, this aldehyde compound 2.12
g was reacted in the same manner as in Example 1 above with 1.63 g of a methylphosphonate in which R ³ in the formula (d) was a phenyl group and R ⁴ was a β-naphthyl group, and the above formula
2.06 g (yield 66%) of the phenanthrene derivative represented by (4) was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis result Calculated value (%) as C ₄₈ H ₃₃ N ₁ (= 623.8): C: 92.42 H: 5.33
N: 2.25 Found (%): C: 92.36 H: 5.29
N: 2.28 Example 5 <Synthesis of Phenanthrene Derivative Represented by Formula (5)> Instead of 9-bromo-10-formylphenanthrene used in Example 1, R ^{5 in} formula (a) was replaced by Phenyl group, R ⁶
Is a hydrogen atom, n = 1, and the same as in Example 1 except that 3.61 g of 3-phenyl-9-bromo-10-formylphenanthrene in which the substitution position of R ⁵ is the 3-position of phenanthrene is used. Thus, 3.55 g (yield 79%) of an aldehyde compound in which R ¹ and R ² in the formula (c) are both phenyl groups, R ⁵ is a phenyl group, and R ⁶ is a hydrogen atom is obtained.

Then, this aldehyde compound 2.25
g is reacted with 1.38 g of methylphosphonic acid ester in which R ³ and R ⁴ in the formula (d) are both phenyl groups in the same manner as in Example 1 above, and is represented by the formula (5) 2.16 g (yield 72%) of a phenanthrene derivative was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis result Calculated value (%) as C ₄₆ H ₃₃ N ₁ (= 599.78): C 92.12 H: 5.55
N: 2.34 Found (%): C: 92.10 H: 5.57
N: 2.36 Example 6 <Synthesis of Phenanthrene Derivative Represented by Formula (6)> Instead of 9-bromo-10-formylphenanthrene used in Example 1, R ⁵ in formula (a), 3,6-dimethyl-9-bromo-1 in which both R ⁶ are methyl groups, n = 1, and the substitution positions of R ⁵ and R ⁶ are the 3- and 6-positions of phenanthrene
In the same manner as in Example 1 except that 3.13 g of 0-formylphenanthrene was used, R ¹ and R ² in the formula (c) were both phenyl groups, and R ⁵ and R ⁶ were both methyl groups. 3.52 g of an aldehyde compound (yield 88%)
Got

Then, this aldehyde compound 2.05
g is reacted with 1.38 g of a methylphosphonic acid ester in which R ³ and R ⁴ in the above formula (d) are both phenyl groups in the same manner as in Example 1 above, and is represented by the above formula (6) 3.49 g (yield 79%) of the phenanthrene derivative was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis result Calculated value (%) as C ₄₂ H ₃₃ N ₁ (= 551.73): C 89.75 H: 7.08
N: 3.17 Found (%): C: 89.72 H: 7.02
N: 3.15 Example 7 <Synthesis of Phenanthrene Derivative Represented by Formula (7)> Instead of the methylphosphonate ester used in Example 1, R ³ in Formula (d) was a phenyl group or R A phenanthrene derivative 1. represented by the above formula (7) was prepared in the same manner as in Example 1 except that 1.39 g of a methylphosphonate in which ⁴ was a pyrrole group and R ⁷ was a methyl group was used.
77 g (yield 71%) was obtained.

The analysis results of the obtained phenanthrene derivative are shown below. Elemental analysis result Calculated value (%) as C ₃₈ H ₂₈ N ₂ (= 497.65): C 91.72 H: 5.47
N: 2.81 Found (%): C: 91.67 H: 5.48
N: 2.78 Example 8 <Synthesis of Phenanthrene Derivative Represented by Formula (8)> Instead of 9-bromo-10-formylphenanthrene used in Example 1, R ⁵ in formula (a), 3,6-dichloro-9-bromo-1 in which both R ⁶ are chlorine atoms, n = 1, and the substitution positions of R ⁵ and R ⁶ are the 3- and 6-positions of phenanthrene
In the same manner as in Example 1 except that 3.54 g of 0-formylphenanthrene was used, R ¹ and R ² in the formula (c) were both phenyl groups, and R ⁵ and R ⁶ were both chlorine atoms. 3.10 g of an aldehyde compound (yield 70%)
Got

Then, the aldehyde compound 2.21
g is reacted with 1.38 g of a methylphosphonate ester in which R ³ and R ⁴ in the formula (d) are both phenyl groups in the same manner as in Example 1 above, and is represented by the formula (8) 2.13 g (yield 72%) of a phenanthrene derivative was obtained. The analysis results of the obtained phenanthrene derivative are shown below.

Elemental analysis result Calculated value (%) as C ₄₀ H ₂₇ N ₁ Cl ₂ (= 592.58): C 81.08 H: 4.59
N: 2.36 Found (%): C: 81.03 H: 4.62
N: 2.38 Examples 9 to 16 and Comparative Example 1 (single-layer type photoreceptor) 8 parts of a perylene pigment represented by the following formula (A) as a charge generating material and obtained in Examples 1 to 8 100 parts of phenanthrene derivative and polycarbonate 100 as a binder resin
And an appropriate amount of methyl chloride to disperse a dispersion to prepare a dispersion, and the obtained dispersion is applied to the surface of an aluminum base tube by a dipping method and dried at 100 ° C. for 1 hour to obtain 20 parts.
A photosensitive layer having a thickness of μm was formed to obtain a positive charging type single-layer type photosensitive member.

[0059]

[Chemical 9]

Comparative Example 1 is a DEH represented by the following formula (B).
Single-layer type photoconductors were produced in the same manner as in Examples 9 to 16 except that 100 parts was used as the charge transport material.

[0061]

[Chemical 10]

With respect to the photoconductors of the above examples and comparative examples,
The following test was performed and the characteristic was evaluated. Measurement of Initial Surface Potential Each photoconductor is loaded into an electrostatic copying tester (Gentec Cynthia 30M, trade name, manufactured by Gentech Co., Ltd.) and the surface thereof is positively charged to obtain an initial surface potential V1s.p. V) was measured.

Measurement of Half-Exposure Amount and Residual Potential The photosensitive member charged in the above-mentioned measurement of the initial surface potential is
Using a halogen lamp, which is the exposure light source of the electrostatic copying tester, the exposure time is 10 lux and the time until the surface potential becomes 1/2 is obtained.
2 (lux · sec) was calculated.

The surface potential was measured 0.5 seconds after the start of the exposure, and the residual potential V1r.p. (V) was measured. Measurement of Light Stability The photoconductor was exposed to an exposure intensity of 5000 using a white fluorescent lamp.
After exposing for 10 minutes under lux condition, same as above,
Initial surface potential V2s.p. (V), residual potential V2r.p. (V)
Was measured. The difference ΔVs.p. (V) from the initial surface potential V1s.p. and the difference ΔV from the residual potential V1r.p.
rp (V) was calculated.

Table 1 shows the above test results.

[0066]

[Table 1]

From these test results, there is almost no difference in the initial surface potential V1 s.p. of the photoconductors of the respective examples from the conventional photoconductor of the comparative example, but the half-exposure amount E1 / Since 2 is small and the residual potential V1r.p. is low, it was found that the sensitivity was remarkably improved. Also,
The photoconductors of the above-mentioned respective examples have almost no difference in ΔVs.p. from the photoconductors of the comparative examples, but since ΔVr.p. is smaller than that of the comparative example, all of them have excellent durability. Was found.

[0068]

INDUSTRIAL APPLICABILITY As described above, the phenanthrene derivative of the present invention has a high charge transporting ability and is excellent in photostability. Therefore, by using this phenanthrene derivative as a charge transporting material, high sensitivity can be obtained. And a photoreceptor having excellent durability can be obtained.

Claims (2)

[Claims] 1. General formula (I): [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents an alkyl group, an aryl group or a heterocyclic group, and R ⁵ ,
R ⁶ is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. n shows the integer of 1-4. ] The phenanthrene derivative represented by these. 2. A photoconductor comprising a conductive layer and a photosensitive layer containing a phenanthrene derivative represented by the general formula (I).