JPS63225660A - 5h-dibenzo(a,d)cycloheptanylidene derivative and 5h-dibenzo(a,d)cycloheptenylidene derivative, production thereof and electrophotographic material obtained by using the same - Google Patents

Abstract

NEW MATERIAL:Compds of formula I (wherein X is -CH2CH2- or -CH=CH-; R<1> and R<2> are each an alkyl, an aralkyl, an arom. ring group or a heterocyclic group; R<3> and R<4> are each H, an alkyl or an alkoxy; Ar1 is an arom. ring group or a heterocyclic group). EXAMPLE:Compd. of formula II. USE:Org. photoconductive materials such as electrophotographic material, electronic plate, photosensor, etc., fluorescent brightener. PREPARATION:A 5H-dibeno[a,d]cycloheptane-5-one derivative of formula III and a 5H-dibenzo[a,d]cycloheptene-5-one derivative are reacted with a dialkyl phosphonate derivative of formula IV in the presence of a basic catalyst (e.g., NaOH) at room temp. to 100 deg.C. The resulting nitro compd. of formula 5 is reacted with a reducing agent (e.g., Na2SO4) to obtain an amino derivative of formula VI. The amino derivative is reacted with a halogen compd. of formula VII in the presence of a basic catalyst at 100-250 deg.C.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides novel 5H-dibenzo[a,d]cycloheptanylidene derivatives and 5H-dibenzo(a,d)cyclohebutenylidene derivatives, their production method, and The present invention relates to an electrophotographic photoreceptor using the same.

The present inventors are actively researching organic photoconductive materials for electrophotographic photoreceptors.
, d] cycloheptenylidene derivatives and 5H-dibenzo(a,d) cycloheptenylidene derivatives, and found that these compounds are extremely useful.

The 5H-dibenzo(a,d)cyclohebutani of the present invention is also useful as an organic photoconductive material for electronic plate making, optical sensors, etc., and can also be used as a fluorescent whitening agent.

[Conventional technology]

Conventionally, inorganic photoconductive materials such as selenium, zinc oxide, and cadmium sulfide have been widely used in photosensitive layers for electrophotography, but in recent years, research has been actively conducted on the use of organic photoconductive materials as electrophotographic photoreceptors. There is.

Here, the basic characteristics required of an electrophotographic photoreceptor are: 1) It should be charged to an appropriate potential by corona discharge in a dark place, 2) It should have a good charge retention rate in a dark place, and 3) Examples include rapid discharge of charges upon irradiation with light, and 4) low residual potential after irradiation with light.

Conventional electrophotographic photoreceptors using inorganic photoconductive materials such as selenium, zinc oxide, and cadmium sulfide have some basic properties, but they are difficult to form, have poor flexibility, and are expensive to manufacture. There are manufacturing problems such as high Furthermore, inorganic photosensitive materials are generally highly toxic, and from this point of view, it is desired to use organic materials instead of inorganic materials for photoreceptors. In general, organic compounds are lighter than inorganic compounds, have excellent film formability and flexibility, and have low manufacturing costs (
Furthermore, it has advantages such as low toxicity.

From the above points, research on electrophotographic photoconductors using organic materials has been actively conducted in recent years, and many electrophotographic photoreceptors using organic materials have been proposed and put into practical use.

By the way, various organic photosensitive polymers including poly-N-vinylcarbazole have been proposed as typical organic electrophotographic photoreceptors that have been proposed up to now, but these polymers are inorganic. Although it is superior in lightness and film formability compared to photoconductive materials, it has poor sensitivity, durability,
It has been difficult to put it into practical use because it is inferior to inorganic photoconductive materials in terms of stability against environmental changes and mechanical strength.

In addition, hydrazone compounds disclosed in U.S. Pat. No. 4,150,987, triarylpyrazoline compounds described in U.S. Pat. No. 3,837,851, etc.,
Low-molecular organic photoconductors such as 9-styrylanthracene compounds described in JP-A No. 4828 and JP-A-51-94829 have been proposed.

By appropriately selecting the binder used, such low-molecular-weight organic photoconductors can overcome the drawbacks of film-forming properties that had been a problem in the field of organic photoconductive polymers. It cannot be said that the sensitivity is sufficient.

For these reasons, a laminated structure in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer has been proposed in recent years. Electrophotographic photoreceptors using this laminated structure as a photosensitive layer can now be improved in terms of sensitivity to visible light, charge retention, surface strength, and the like. Such electrophotographic photoreceptors are disclosed in, for example, U.S. Pat. No. 3,837,851, U.S. Pat.
It is disclosed in Japanese Patent Application Laid-Open No. 55-161247.

However, in electrophotographic photoreceptors that use conventional low-molecular organic photoconductors in the charge transport layer, the sensitivity and characteristics are not necessarily sufficient, and the brightness does not improve after repeated charging and exposure. There is a point that needs to be greatly improved in terms of fluctuations in the part potential and the dark part potential.

[Problem that the invention seeks to solve]

It is an object of the present invention to provide new compounds which overcome the drawbacks or disadvantages of the photoconductive materials mentioned above. Another object of the present invention is to provide a novel organic photoconductor.

Still another object of the present invention is to provide a novel charge transport material in a laminated photosensitive layer in which a charge generation layer and a charge transport layer are functionally separated.

[Means for solving problems]

That is, the present invention is a 5H-dipenzo(a,d)cycloheptenylidene derivative and a 6H-dibenzo(a,d)cycloheptenylidene derivative represented by the general formula [I1].

In the formula, X represents -CH2CH2- or -0H=CH-. R1 and R2 represent an alkyl group, an aralkyl group, an aromatic ring group, or a heterocyclic group, specifically, an alkyl group such as methyl, ethyl, propyl, an aralkyl group such as benzyl, phenethyl, naphthylmethyl, phenyl, naphthyl, etc. represents an aromatic ring group or a heterocyclic group such as pyridyl, quinolyl, chenyl, furyl, etc. These alkyl groups, aralkyl groups, aromatic ring groups and heterocyclic groups may have substituents, such as alkyl groups such as methyl, ethyl, propyl, etc. an alkoxy group, a halogen atom such as fluorine, chlorine, or bromine, or a nitro group.

R8 and R4 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom;
Specific examples of the halogen atom are the same as above. The alkyl group and alkoxy group may have the above-mentioned substituents. Arl represents an aromatic ring group or a heterocyclic group, and specific examples of these aromatic ring groups and heterocyclic groups are the same as above. These aromatic ring groups and heterocyclic groups may have a substituent, for example, the alkyl group, alkoxy group,
Examples include halogen atoms and nitro groups.

Further, the present invention relates to an amino derivative represented by the general formula [IV] and the following general formula [V]R'-Y
5H-dibenzo[a,d]cycloheptanylidene derivatives and 5H-dibenzo(a,d)cycloheptanylidene derivatives represented by the general formula [I] by reacting with a halogen compound represented by [V] It is a manufacturing method.

In the formula, X represents -CH2CH2- or -CH=CH-. R', R'', R'', R4 and Ar are as defined above. R6 represents an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group, specifically, methyl,
It represents alkyl groups such as ethyl and propyl, aralkyl groups such as benzyl, phenethyl and naphthylmethyl, aromatic ring groups such as phenyl and naphthyl, and heterocyclic groups such as pyridyl, quinolyl and furyl. Furthermore, these alkyl groups, aracyl groups, aromatic ring groups and heterocyclic groups may have substituents,
Examples of the substituent include an alkyl group such as methyl, ethyl, and propyl, an alkoxy group such as methoxy, nidoxy, and propoxy, or a halogen atom such as fluorine, chlorine, and bromine, or a nitro group. Moreover, Y represents chlorine, bromine or iodine.

Further, the present invention is an electrophotographic photoreceptor characterized by having a layer containing a compound represented by the general formula [I].

In the formula, X represents -CH2CH2- or -CH=CH-.

R1 and R2 represent an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group, specifically methyl, ethyl,
It represents an alkyl group such as propyl, an aralkyl group such as benzyl, phenethyl, naphthylmethyl, an aromatic ring group such as phenyl, naphthyl, or a heterocyclic group such as pyridyl, quinolyl, chenyl, furyl.

Furthermore, these alkyl groups, aralkyl groups, aromatic ring groups and heterocyclic groups may have substituents (for example, alkyl groups such as methyl, ethyl, propyl, methoxy, ethoxy, propoxy, etc.). an alkoxy group, a halogen atom such as fluorine, chlorine, bromine, or a nitro group.

Further, Rs and R4 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. Specific examples of the alkyl group and alkoxy group are the same as above. Further, the alkyl group and alkoxy group may have the above-mentioned substituents.

Arl represents an aromatic ring group or a heterocyclic group, specifically an aromatic ring group such as phenyl or naphthyl, or a heterocyclic group such as pyridyl, quinolyl, chenyl, or furyl. The aromatic ring group and the heterocyclic group may have a substituent. This Ar,
Examples of substituents that may have include alkyl groups such as methyl, ethyl, and propyl, methoxy, ethoxy,
Examples include alkoxy groups such as propoxy, halogen atoms such as fluorine, chlorine, and bromine, and nitro groups.

The amino derivative represented by the general formula [IV] used in the present invention is generally synthesized by the following reaction route.

[IV] [In the formula, X, R'', R' and Arl have the same meanings as above. Also, R7 represents an alkyl group having 1 to 4 carbon atoms]
i.e. 5H-dibenzo(a,d)cyclohebutane-5
-one derivative and 5H-dibenzo(a,d)cyclohebuten-5-one derivative [Vll and dialkyl phosphonate derivative [VII] are reacted in the presence of a basic catalyst at a temperature from room temperature to about 100°C [ VIII
] to obtain the nitro form. Examples of the basic catalyst include caustic soda, caustic potash, sodium amide, sodium hydride, methyllithium, n-butyllithium, and alcolades such as sodium methylate and potassium t-butoxide. In addition, as a reaction solvent, methanol, ethanol, butanol, 2-methoxyethanol,
Examples include 1,2-dimethoxyethane, dioxane, tetrahydrofuran, diethyl ether, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, and the like. Among these, polar solvents such as dimethyl sulfoxide and N,N-dimethylformamide are often preferred. Further, the dialkyl phosphonate derivative [VII] is generally easily synthesized by any of the following reaction routes.

Ar1-CH2Z + P(OR')3 A
r1-CH2F(OR2[IX]
[X]↓Nitration No 2-Ar, -CH2Z + P (OR')
3- [VII] '[XI] [In the formula, Arl and R' have the same meanings as above. Also Z
represents a halogen atom such as chlorine, bromine or iodine] In other words, the corresponding halomethyl compounds [IX] and [XI
] with trialkyl phosphite directly or in a solvent such as toluene or xylene to form [X] and Q[V
In the case of [X], [Vll ] can be easily obtained by further conventional nitration.

Here, the trialkyl phosphite is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group.

The nitro compound [VII] obtained in the above manner can be treated with conventional reducing agents such as iron, zinc, sodium sulfite, sulfur,
The amino derivative represented by the general formula [IV] can be obtained using sodium hydrogen sulfide, sodium dithionate, hydrazine, or the like.

The amino derivative represented by the general formula [IV] obtained in this way is reacted with a halogen compound represented by the general formula [V] in the presence of a base catalyst.
] 5H-dibenzo(a,d)cycloheptenylidene derivatives and 5H-dibenzo(a,d)cycloheptenylidene derivatives can be obtained.

Generally, when R6 is an alkyl group or an aralkyl group, examples of the basic catalyst include caustic soda, caustic potash, sodium amide, sodium hydride, and alcoholades such as sodium methylate and potassium t-butoxide. In addition, as a reaction solvent, methanol, ethanol, butanol, 2-methoxyethanol, 1,2
-dimethoxyethane, dioxane, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N
, N-dimethylformamide, etc., and the reaction temperature depends on 1) the stability of the basic catalyst of the solvent used, and 2
) Although the temperature is selected from a wide range depending on the reactivity of the reaction components (compounds of general formulas [IV] and [V]), the temperature is actually from room temperature to 140°C, preferably from room temperature to about 80°C. On the other hand, R
When 6 is an aromatic ring or a heterocycle, R6 is generally as described above.
In most cases, it does not react under the same reaction conditions as for alkyl and aralkyl, but it can be synthesized by the following reaction.

Potassium carbonate, sodium carbonate, sodium hydride, etc. are used as basic catalysts, and N,N-dimethylformamide, dimethylsulfoxide, P-cymene, etc. are used as reaction solvents.
Using O-dichlorobenzene, nitrobenzene, etc., 10
The reaction is carried out by heating to about 0°C to 250°C. In some cases, the reaction may be carried out without using a solvent. The reaction temperature is selected within a wide range depending on the reactivity of the reaction components (compounds of general formulas ['IV] and [V]). In many cases, it is preferable to carry out the reaction by adding a catalyst such as ordinary steel or copper oxide.

However, when the reaction time is shortened or a compound with poor reactivity is used, the reaction may be carried out at a higher temperature or at a higher pressure using an autoclave or the like.

The novel 5H- related to the present invention obtained in this way
Dibenzo[a,d]cycloheptanylidene derivative and 5
Examples of H-dibenzo(a,d)cyclohebutenylidene derivatives are as follows.

<Compound Examples> In addition to the above-mentioned synthesis methods, the novel compounds of the present invention can be synthesized by
It can also be synthesized by the method shown below.

Synthesis example of exemplified compound (13) p-ditolyl aminobenzaldehyde 20g (66,4
mmol) and 10.11-dihydro-5H-dibenzo I
: a, d) 23.1 g of cycloheptenyl phosphonate (
69,9m mol) as DMS 0100c
Oily sodium hydride (60%) dissolved in c at room temperature 2
．． Add 8g (70,0mmol), then oil bath approx.
The mixture was heated and stirred at 00°C for 10 hours. After cooling, the reaction solution was poured into water, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and the residue was recrystallized with a methanol-acetone mixed solvent to obtain the target compound. 13.7g of (13) was obtained. Yield 46.1%.

Elemental analysis results> Calculated value (%) Measured value (%) C90,5390,50 H6,546,56 N 2.93 2.94λ max
(THF) 357.4HmThe novel 5H-dibenzo(a,d)cycloheptenylidene derivatives and 5H-dibenzo(a,d)cycloheptenylidene derivatives obtained in this manner are highly sensitive to light in electrophotographic photoreceptors. Extremely useful as a conductive material.

In a preferred embodiment of the present invention, a compound represented by the above general formula can be used as a charge transport material in an electrophotographic photoreceptor in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer.

Further, particularly good results can be obtained when a compound in which R1 and R2 of the substituted amino group of general formula (1) are both aromatic ring groups is used as the charge transport material.

The charge transport layer is preferably formed by applying a solution prepared by dissolving the compound represented by the above general formula and a binder in a suitable solvent and drying the solution. Examples of the binder used here include polyarylate resin, polysulfone resin, polyamide resin, acrylic resin, acrylonitrile resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, phenol resin, epoxy resin, polyester resin, alkyd resin, and polycarbonate. , polyurethane, or copolymer resins containing two or more repeating units of these resins, such as styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copyrimer, and the like. In addition to such insulating polymers, organic photoconductive polymers such as polyvinylcarbazole, polyvinylanthracene, and polyvinylpyrene can also be used.

The blending ratio of the binder and the charge transport material of the present invention is preferably 10 to 500 parts by weight of the charge transport material per 100 parts by weight of the binder.

The charge transport layer is electrically connected to the charge generation layer below and has the function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. ing. At this time, this charge transport layer may be laminated on or under the charge generation layer. However, it is desirable that the charge transport layer is laminated on the charge generation layer. This charge transport layer cannot be made thicker than necessary because there is a limit to its ability to transport charge carriers.

Generally, it is 5 to 30 μm, but the preferred range is 8 μm.
~20 μm.

The organic solvent used when forming such an electric field transport layer is
The binder varies depending on the type of binder used, and it is preferable to select one that does not dissolve the charge generation layer or underlying subbing layer. Specific organic solvents include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide. sulfoxides such as, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate,
Aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, etc., or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. .

Coating methods include dip coating, spray coating, spinner coating, bead coating,
This can be carried out using a coating method such as a Mayer bar coating method, a blade coating method, a roller coating method, or a curtain coating method. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying can be carried out at a temperature of 30° C. to 200° C. for a period of time ranging from 5 minutes to 2 hours, either stationary or under ventilation.

The charge transport layer of the present invention can contain various additives. Such additives include diphenyl, diphenyl chloride, 0-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, benzophenone, compacted paraffin, diuralyl thioprobionate. , 3,5-dinitrosalicylic acid, and various fluorocarbons.

The charge generation layer used in the present invention is made of inorganic charge generation substances such as selenium, selenium-tellurium, amorphous zircon, etc., biryllium dyes, thiapyrylium dyes, azulenium dyes, thiacyanine dyes, quinocyanine dyes, azulenium dyes, etc. Organic charge generation such as cationic dyes, squbarium salt dyes, phthalocyanine pigments, anthorone pigments, dibenzpyrenequinone pigments, polycyclic quinone pigments such as vilanthrone pigments, indigo pigments, quinacridone pigments, azo pigments, etc. Separate deposited or applied layers of selected materials can be used.

Among the charge-generating substances used in the present invention, there are a wide variety of azo pigments in particular, and it is difficult to specify their structures, but examples of structures of particularly effective azo pigments are shown below.

The general formula of an azo pigment is as shown below, with the central skeleton being A.

A1000N=N-Cp)n If we express part of the coupler as Cp (here n=2゜o
r 3 ), first, specific examples of A include the following.

C2H3 A-18+CH=N-N=CH-@)- Also, specific examples of Cp include. The central skeleton A and the coupler Cp form a pigment serving as a charge-generating substance by appropriate combination.

The charge-generating layer can be formed by dispersing the above-mentioned charge-generating substance in a suitable binding portion and coating it on a support, or can be obtained by forming a vapor-deposited film using a vacuum vapor deposition device. Can be done. The binder used to form the charge generating layer by coating can be selected from a wide variety of insulating resins and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. can. Preferably polyvinyl butyral, polyarylate (bisphenol A
polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol, polyvinylpyrrolidone Insulating resins such as

The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less. Examples of organic solvents used during coating include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide, and N.

Amides such as N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethyls such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene, and tetrachloride. Carbon, aliphatic halogenated hydrocarbons such as trichloroethylene, or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used.

Coating methods include dip coating, spray coating, spinner coating, bead coating,
This can be carried out using a coating method such as a Mayer bar coating method, a blade coating method, a roller coating method, or a curtain coating method.

The charge generation layer contains as much of the organic photoconductor as possible in order to obtain sufficient absorbance and is a thin film layer, for example 5 μm, in order to shorten the range of the generated charge carriers.
Hereinafter, it is preferable to use a thin film layer having a thickness of preferably 0.01 to 1 μm. This means that most of the incident light is absorbed by the charge generation layer, generating a large number of charge carriers, and that the generated charge carriers are not deactivated by recombination or trapping (charge transport This is due to the need to inject into the layer.

A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a conductive support.

As the conductive support, the support itself is conductive, such as aluminum, aluminum alloy, copper, zinc,
Stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, platinum, etc. can be used, and in addition, aluminum, aluminum alloy, indium oxide, tin oxide, indium oxide-tin oxide alloy, etc. can be coated by vacuum evaporation method. Plastics with formed layers (e.g. polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resins, porfluoroethylene, etc.), conductive particles (e.g.
A support in which plastic or the above conductive support is coated with aluminum powder, titanium oxide, tin oxide, zinc oxide, carbon black, silver particles, etc.) together with a suitable binder, and a support in which plastic or paper is impregnated with conductive particles. Plastics having conductive polymers, etc. can be used.

A subbing layer having barrier and adhesive functions can also be provided between the conductive support and the photosensitive layer. The undercoat layer is made of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, (nylon 6, nylon 66, nylon 610, copolymerized nylon,
(alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc.

The thickness of the subbing layer is 0.1 to 5 μm, preferably 0.5 to 5 μm.
3 μm is appropriate.

When using a photoreceptor in which a conductive support, a charge generation layer, and a charge transport layer are laminated in this order, the charge transport material has hole transport properties, so the surface of the charge transport layer must be negatively charged. During post-exposure, holes generated in the charge generation layer in the exposed area are injected into the charge transport layer, and then reach the surface and neutralize the negative charge, resulting in attenuation of the surface potential and an electrostatic contrast between the exposed area and the unexposed area. occurs. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transport material is used.

The electrophotographic photoreceptor of the present invention can be used not only for electrophotographic copying machines, but also for laser printers, CRT printers,
According to the present invention, it is possible to provide an electrophotographic photoreceptor with high sensitivity, and there is also an advantage that fluctuations in bright area potential and dark area potential are small when charging and exposure are repeatedly performed. are doing.

Hereinafter, the present invention will be explained according to examples.

<Example 1> (Synthesis of exemplified compound (39)) Benzyl chloride (d=1.10) 154 ml (1,34
mole) and triethyl phosphite (d=0.969) 20
6mj! (1.2 mol) was gradually heated in an oil bath while stirring, and the oil bath was maintained at around 160 to 180° C. and stirred under reflux for 20 hours.

After the reaction, vacuum distillation was performed to obtain 215.4 g of diethylbenzyl phosphonate (yield 78.6%). The boiling point is 134.
The temperature was 5 to 136.0°C (7 mm Hg). The infrared absorption spectrum (neat method) is shown in FIG.

Next, fuming nitric acid (d=1.52.94%) 55.0m!
! (1.25 mol) to 200mj! After stirring and cooling the internal temperature to -10 to -5°C, 61.6 g of diethylbenzyl phosphonate (0
, 27 mol) was slowly added dropwise over 1 hour. After the addition was completed, the mixture was stirred at the same temperature for 30 minutes, and the reaction mixture was poured into 600 mf of ice water and extracted with about 300 ml of ethyl acetate. The organic layer was further washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.

Further, the residue was distilled under reduced pressure to obtain 61.3 g of diethyl-4-nitrobenzyl phosphonate (yield: 83.1%).
. The boiling point was 199-201.0°C (3 mm Hg). Elemental analysis value is CIIH16NO! The IP was as follows.

0% N% N% Calculated value 48.36 5,90 5.13 Actual value 4
8.39 5,92 5.10 Infrared absorption spectrum (
neat method) is shown in FIG.

Oily sodium hydride (approximately 60%) (3.60 g So mmol) is added to 150 m 12 of dimethyl sulfoxide at room temperature. After the addition was completed, the mixture was heated in an oil bath to an internal temperature of around 70°C and stirred for about 1 hour. Thereafter, the reaction solution was cooled to room temperature, and 25.1 g (92 mmol) of the previously obtained diethyl-4-nitropenzylphosphoone) and 10. A solution of Og (48.5 mmol) in 50 ml of dimethyl sulfoxide was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 15 minutes, and then heated and stirred for 2 hours while maintaining the internal temperature at 70 to 80° C. in an oil bath. After the reaction was completed, the mixture was cooled to room temperature, poured into saturated saline solution (11), and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure.

Methanol was added to the residue, the precipitated crystals were collected by filtration, and the obtained crystals were recrystallized with a methanol-acetone mixed solvent. .94g (yield 69.3%) was obtained.The melting point was 151.5-152.5°C.

The elemental bone value was as follows as Cz2H+5NO2.

0% N% N% Calculated value 81,21 4.65 4.30 Actual value
81.18 4.69 4.31 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

5-(4-nitrobenzylidene')-5H-dibenzo[
'a, d] cycloheptene 10. Og (30.7 mmol), reduced iron powder 8.0 g (143 mmol), concentrated hydrochloric acid (d=1.18°35%) 2.70 mj! (30,
6 mmol) in 150 m N,N-dimethylformamide
! ! In addition, the mixture was heated to bring the internal temperature to around 70°C, and heated and stirred at that temperature for 3 hours. After the reaction is completed, cool in an ice water bath and add approximately 12.4 mj7 of 10% caustic soda aqueous solution.
was added and stirred, followed by suction filtration, and the filtrate was diluted with saturated saline solution about I!
! After drying the organic layer with anhydrous sodium sulfate, the solvent was removed under reduced pressure, methanol was added to the residue, the precipitated crystals were collected by filtration, and the obtained crystals were recrystallized from methanol. 5-(4-aminobenzylidene)
-5H-dibenzo(a,d)cycloheptene at 8.4
1 g was obtained (yield 92.7%).

The melting point was 119-120.0°C. Elemental analysis is C2
2H17N was as follows.

0% N% N% Calculated value 89.46 5.80 4.74 Actual value
89.41 5.83 4.76 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Previously obtained 5-(4-aminobenzylidene)-5H-
Dibenzo[:a,d]cycloheptene 7.90g (26
, 7 mmol), p-iodotoluene 22.0 g (10
1 mmol) anhydrous potassium carbonate 11.0 g (79,6
mmol) and 2.2 g of copper powder into O-dichlorobenzene 3
The mixture was stirred under reflux for 7 hours in an oil bath maintained at around 190°C. After completion of the reaction, the reaction solution was suction filtered, the filtrate was washed successively with 3-5% aqueous sodium thiosulfate solution and saturated brine, and the organic layer was dried over anhydrous sodium sulfate.
Solvent was removed under reduced pressure.

Approximately 60 m i of acetone to the residue! was added, the precipitated crystals were collected by filtration, and recrystallized using a mixed solvent of ethyl acetate and 7n-hexane to obtain 5(4-(J-p-)lylamino).
Benzylidene]-3H-dibenzo(a,d)cycloheptene (9.52 g) was obtained (yield: 75.0%).

Melting point is 168. The ON temperature was 169.0°C, and the elemental analysis was as follows as C36H29N.

0% N% N% Calculated value 90.90 6.15 2.95 Actual value
90.85 6.17 2.98 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 2> (Synthesis of Exemplified Compound (36)) 10.0 g of 5-(4-aminobenzylidene')-3H-dibenzo(a,d)cycloheptene (33,9 42.0 g (206 mmol) of iodobenzene, 14.1 g (102 mmol) of anhydrous potassium carbonate, and 2.80 g of copper powder.
The mixture was stirred under reflux for 4 hours in an oil bath kept at around 200°C. After the reaction is completed, the reaction solution is suction filtered and the filtrate is reduced to 3-5%.
The organic layer was washed successively with an aqueous sodium thiosulfate solution and a saturated saline solution, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Approximately 80 mj+ of methanol was added to the residue, the precipitated crystals were collected by filtration, and further recrystallized using a methanol-acetone mixed solvent to obtain 5-(4-diphenylaminobenzylidene)-5H-dibenzo[a,d]cycloheptene. .2g was obtained. (Yield 73.8%).

The melting point was 83.5-84.5°C. Elemental analysis is C3
It was as follows as 4H25N.

0% N% N% Calculated value 91.24 5.63 3.13 Actual value
91.27 5,64 3.29 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 3> (Synthesis of Exemplified Compound (27)) 5-(4-aminobenzylidene) 5H-dibenzo[a,d]cycloheptene 8 obtained in the same manner as in Example 1
．． Og (27.1 mmol) in 30 mj of N,N-dimethylformamide! In addition, 3.25 g (about 81.3 mmol) of oily sodium hydride (about 60%) was slowly added thereto at room temperature. After the addition was complete, the mixture was stirred for 15 minutes at room temperature, and then 12.6 g of ethyl iodide (80,8
mmol) and stirred at room temperature for 30 minutes, then stirred at room temperature for 2 hours at 80°C.
The reaction was carried out at °C. After cooling to room temperature, the reaction solution was added with about 200mj of saturated saline! and extracted with ethyl acetate. After drying the organic layer over anhydrous sodium sulfate, the solvent was removed under reduced pressure, about 60 ml of methanol was added to the residue, the precipitated crystals were collected by filtration, and further recrystallized using a methanol-acetone mixed solvent to give 5-(4 -diethylaminobenzylidene) -3H-dibenzo(a,d)cycloheptene 7
．． 91g was obtained (yield 83.0%). Melting point is 109.0 ~
The temperature was 110.0°C.

The elemental analysis was as follows as C26H25N.

0% N% N% Calculated value 88.85 7.17 3.98 Actual value
88.81 7.19 3.40 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 4> (Synthesis of Exemplified Compound (13)) 5H-dibenzo(a,d)cyclohebutene- of Example 1
5-(
4-aminobenzylidene)-5H-dibenzo(a,d)
5.0 g (16.8 mmol) of cyclohebutane, p-
Iodotoluene 14.0g (64.2 mmol), anhydrous potassium carbonate 7,0g (50.6 mmol) and copper powder 1.4g, nitrobenzene 15mj! In addition, the mixture was stirred under reflux for 5 hours. After the reaction was completed, the reaction solution was filtered under suction, the filtrate was washed successively with 3-5% aqueous sodium thiosulfate solution and saturated brine, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Approximately 50 ml of n-hexane was added to the residue, the precipitated crystals were collected by filtration, and recrystallized using a mixed solvent of ethyl acetate and n-hexane to obtain 5-(4
5.9 g of -(di-p-tolylamino)benzylidene]-3H-dibenzo[a,d)cycloheptane was obtained (yield 73.5%). The melting point was 158.5-159.7°C. The elemental analysis was as follows as 036H31N.

0% N% N% Calculated value 90.53 6.54 2.93 Actual value
90.50 6.56 2.94 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 5> (Synthesis of Exemplary Compound (1)) 5-(4-aminobenzylidene)-5H-dibenzo[a,d]cycloheptane 5.0 g (16,8 To 20 ml of tetrahydrofuran was added 2.1 g (about 52.5 mmol) of oily sodium hydride (about 60%) at room temperature. After the addition was completed, the mixture was stirred at room temperature for 10 minutes, then 9.54 g (67.2 mmol) of methyl iodide was added, stirred at room temperature for 15 minutes, and heated under reflux for 3 hours. After cooling to room temperature, add about 100ml of water to the reaction solution! The precipitated crystals were collected by filtration, and further diluted with isopropyl ether.
Recrystallization was performed from ethyl acetate to obtain 4.37 g of 5-(4-dimethylaminobenzylidene)-5H-dibenzo(a,d)cycloheptene (yield: 79.9%). The elemental analysis was as follows as C24H23N.

0% N% N% Calculated value 88.58 7.12 4.30 Actual value 88.54 7.12 4.34 <Example 6> (Synthesis of exemplified compound (52)) Obtained in the same manner as Example 1 5-(4-aminobenzylidene)-5)/-dibenzo(a,d)cycloheptene lo,og (33,9 mmol) and acetic anhydride 4.1
5 g (40.6 mmol) was added to 50 ml of toluene and heated under reflux for 3 hours. After cooling, the reaction solution was diluted with 200% water.
mj? 5-(4-acetylaminobenzylidene)-5H-dibenzo(a,d)cycloheptene was collected by filtration and further washed with water and methanol.
．． 6g was obtained (yield 92.7%). Melting point is 125.0-1
The temperature was 26.0°C. The infrared absorption spectrum (KBr tablet method) is shown in FIG.

5-(4-acetylaminobenzylidene) obtained above
-5H-dibenzo(a, d)cycloheptene 8.0g
(23.7 mmol), p-iodotoluene 7.75
g (35,5 mmol), anhydrous potassium carbonate 3.70
g (26.8 mmol) and 1.80 g of copper powder to 15 mj of p-cymene! In addition, reflux stirring was performed for 5 hours. After the reaction was completed, the reaction solution was filtered under suction, the filtrate was washed successively with 3-5% sodium thiosulfate aqueous solution and saturated brine, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. 40mj of tetrahydrofuran! Sodium methylate 2,70 g (50,0 mmol) dissolved in and at room temperature
was added, and after stirring at room temperature for 1 hour, the reaction solution was diluted with 1 part of water.
50 mjl! 5-(4-(p-tolylamino)benzylidene)-
57-/-dibenzo(a,d]cycloheptene 5.8
1 g was obtained (yield 63.6%).

The melting point was 174.0-175.0°C. The elemental analysis was as follows as C29H23N.

0% N% N% Calculated value 90.35 6.01 3.63 Actual value
90.34 6.00 3.66 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

Furthermore, 5.0 g (13.0 mmol) of 5-(4-(p-tolylamino)benzylidene)-5H-dibenzo[a,d]cycloheptene obtained above was added to 15 ml of N,N-dimethylformamide, and added thereto. At room temperature, 0.63'g (approximately 15.8 mmol) of oily sodium hydride (approximately 60%) was added slowly. After the addition was complete, the mixture was stirred for 15 minutes at room temperature, and 3.34 g (19
, 5 mmol) and the reaction was carried out at 80°C for 3 hours.

After cooling the reaction solution, add 130 mj of water! The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was separated and purified using a silica gel column to obtain 5-[4-(N-benzyl-P-tolylamino)benzylidene] -3H-dibenzo[a, d)
5.10 g of cycloheptene was obtained (yield 82.5%).

The melting point was 59.0-60.0°C. Elemental analysis is C3
It was as follows as 6H29N.

0%, N% N% Calculated value 90.91 6.15 2.94 Actual value
90.87 6.18 2.95 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 7> (Synthesis of Exemplified Compound (51)) 5-[4-(N-p-tolylamino)benzylidene]-3H-dibenzo(a,
d] cycloheptene 5.0 g (13.0 mmol),
10.6 g (52.0 mmol) of iodobenzene, 3.05 g (22.1 mmol) of anhydrous potassium carbonate, and 0.60 g of copper powder were stirred under reflux for 5 hours in an oil bath. After the reaction was completed, the reaction solution was suction filtered, the filtrate was washed successively with 3-5% aqueous sodium thiosulfate solution and saturated brine, the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure.

The residual camellia was separated and purified using a silica gel column, and 5-
(4-(N-phenyl-p-)lylamino)benzylidene] -3H-dibenzo(a,d)cycloheptene with 4
．． 62g was obtained (yield 77.0%).

The melting point was 52.0-53.0°C. Elemental analysis is C3
5Hrr N was as follows.

0% N% N% Calculated value 91.07 5.90 3.03 Actual value
91.11 5.87 3.02 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 8> (Synthesis of Exemplary Compound (32)) 5.0 g of 5-(4-acetylaminobenzylidene)-5H-dibenzo(a,d)cycloheptene (14,8 mmol) was added to 15 ml of N,N-dimethylformamide, 0.64 g (approximately 16 mmol) of oily sodium hydride (approximately 60%) was added thereto at room temperature, and after stirring at room temperature for 15 minutes, 2-chloropyridine was added. After adding 1.82 g (16.0 mmol) and stirring at room temperature for 30 minutes, the mixture was heated and stirred at 100° C. for 2 hours.

After cooling, the reaction solution was poured into 100 mA of water, and the precipitated crystals were collected by filtration and dissolved in 30 mA of tetrahydrofuran. 0.84 g (15.5 mmol) of sodium methylate was added at room temperature, and the reaction solution was stirred for 1 hour at room temperature. water 100
The precipitated crystals were collected by filtration and further recrystallized with ethanol to obtain 3.8 g of 5-(4-(2'-pyridylamino)benzylidene]-3H-dibenzo(a, d:1 cycloheptene). rate 79.2) then this obtained 5
-(4-(2'-pyridylamino)benzylidene)-5
H-dibenzo(a,b)cycloheptene 3.0g (8
, 1 mmol) to 15 mf of tetrahydrofuran,
Add oily sodium hydride (approximately 60%) to it at room temperature.
35 g (approximately 868 mmol) was slowly added, and after stirring at room temperature for 15 minutes, 1.85 g (11,
9 mmol) was added thereto and stirred under reflux for 3 hours. After cooling, the reaction solution was poured into 100 mf of water, the precipitated crystals were collected by filtration, and further recrystallized using a methanol-acetone mixed solvent to obtain 5-(4-(N-ethyl-2'-pyridylamino)benzylidene]-3H. -1.92g of dibenzo(a,d)cycloheptene was obtained (yield 59.2%).Elemental analysis showed that Cn
The H24N2 was as follows.

0% N% N% Calculated value 86.97 6.04 6.99 Actual value
86.94 6.01 7.05 <Example 9> (Synthesis of Exemplary Compound (53)) Diethyl-2-nitropenzyl phosphonate synthesized from 2-nitrobenzyl bromide and triethyl phosphite was used as an example. 5-(4-(di-0-tolylamino)benzylidene)-3H-dibenzo(a , d) 8.91 g of cycloheptene was obtained (yield 70.2%). Melting point is 153
．． The temperature was 0 to 154.0°C.

The elemental analysis was as follows as 038H29N.

0% N% N% Calculated value 90.90 6.15 2.95 Actual value
90.86 6.17 2.97 The infrared absorption spectrum (KBr tablet method) is shown in FIG.

<Example 10> β-type copper phthalocyanine (trade name: Lionol Blue NCB Toner) manufactured by Toyo Ink Manufacturing Co., Ltd.
) was refluxed in water, ethanol and benzene sequentially, and filtered to purify the pigment.
)" 14 g;) 35 g of toluene; and 35 g of dioxane were mixed and dispersed in a ball mill for 6 hours to prepare a coating solution. This coating liquid was applied onto an aluminum sheet using a Meyer bar to give a dry film thickness of 0.5 μm to form a charge generation layer.

Next, 7 g of the above-mentioned exemplified compound (12) as a charge transport compound and 7 g of polycarbonate resin (trade name "Panlite 11500J" manufactured by Yojin Kasei Co., Ltd.) were dissolved with stirring in a mixed solvent of 35 g of tetrahydrofuran and 35 g of chlorobenzene. The resulting solution was applied onto the charge generation layer using a Mayer bar so that the dry film thickness was 11 μm.
An electrophotographic photoreceptor with a photosensitive layer consisting of a layered structure was prepared.

The electrophotographic photoreceptor produced in this way was sold to Kawaguchi Electric Co., Ltd.
Electrostatic copying paper tester Model-3P-428 was used to statically charge the corona at -3 KV, and the test was carried out at 1 KV in the dark.
After being held for a second, it was exposed to light at an illuminance of 251 ux and the charging characteristics were examined.

The charging characteristics include the surface potential (VO) and the amount of light exposure required to attenuate the potential (vl) after dark decay for 1 second to
8%) was measured.

Furthermore, in order to measure the fluctuations in bright area potential and dark area potential during repeated use, the photoreceptor prepared in this example was attached to the photosensitive drum cylinder of a PPC copier NP-150Z manufactured by Canon Inc. , 50,000 copies were made using the same machine, and changes in bright area potential (VL) and dark area potential (Vo) were measured at the initial stage and after 50,000 copies were made.

Table-1 <Examples 11-25. Comparative Examples 1 to 5> In each of these Examples, Exemplified Compound (1) (4) (5) (7) (11) ( 1
3) (16) (17) (ts) (at) (38
) (39) (41) (45) (48) and a pigment with the following structure as the charge generating substance.
An electrophotographic photoreceptor was produced in the same manner as in Example 10.

The electrophotographic properties of each photoreceptor were measured in the same manner as in Example 1O. The results are shown below.

For comparison, an electrophotographic photoreceptor was prepared in the same manner using a compound having the structure shown below as a charge transport compound, and its electrophotographic properties were measured.

2H6 E% vD vl ゛ 6 ” lux@sec -I
ζru −Iζru 11 (1) 1
．． 8 698 68912 (4)
1.8 699 69113
(5) 1.7 693
68514 (7) 1.7
695 68415 (11)
0.9 697 69216 (1
3) 1.0 699 6901
7 (16) 1.1 698
68318 (17) 1.1
693 68019 (18)
1.0 694 68320 (31
) 2.0 694 68521
(38) 1.2 694
68522 (39) 1.0
699 68823 (41) 0
．． 9 698 68524 (45)
1.2 694 68825
(48) 2.2 693
685mm EI V
Vl 1 3.5
695 6852 2
1.6 697 6903
3 4.5 700 6
924 4 7.0
692 6805 5 2
．． 3 698 689 early
Example after 50,000 sheets durability v.
vL vo vL-Volt - Porto - Porto - Volt Early Years
After 50,000 sheets durability v v
v vl 698 190
648 283 From the above results, it can be seen that the compound of the present invention has improved sensitivity compared to the comparative compound, and in particular, has excellent stability with significantly less potential fluctuation due to repetition.

<Example 26> An ammonium aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water) was placed on an aluminum cylinder.
, water 222mj? ) by dip coating method,
It was dried to form a subbing layer with a coating weight of 1.0 g/d.

Next, 1 part by weight of a charge generating substance having the following structure, 1 part by weight of butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.) and 30 parts by weight of isopropyl alcohol were dispersed for 4 hours using a ball mill disperser. This dispersion was applied onto the previously formed subbing layer by a dip coating method and dried to form a charge generating layer. The film thickness at this time was 0.3 μm.

Next, 1 part by weight of the above-mentioned charge transport compound No. (14), 1 part by weight of polysulfone resin (P1700, manufactured by Union Carbide), and 6 parts by weight of monochlorobenzene were mixed and dissolved by stirring with a stirrer. This liquid was applied onto the charge generation layer by dip coating and dried to form a charge transport layer. The film thickness at this time was 12 μm.

A corona discharge of 13 KV was applied to the photoreceptor thus prepared. The surface potential at this time was measured (initial potential VO). Furthermore, the surface potential of this photoreceptor was measured after it was left in a dark place for 5 seconds. Sensitivity was evaluated by measuring the exposure amount (E% μJ/crt) required to attenuate the potential V after dark decay. At this time, a gallium/aluminum/propylene ternary semiconductor laser (output power: 5 mw; oscillation wavelength: 780 nm) was used as a light source. These results were as follows.

V,: -697 volts Next, a laser beam printer (a reversal development type electrophotographic printer equipped with the same semiconductor laser as above) (
The above photoreceptor was set in a Canon LBP-CX), and an actual image forming test was performed.

The conditions are as follows. -Surface potential knee 7 after next charging
00V, surface potential after image exposure; -130V (exposure amount 2.0 μJ/cr+f) transfer potential +700V, developer polarity; negative polarity, process speed; 50 mm/sec
, development conditions (development bias); -430V, image exposure scan method; image scan, - exposure before next charging; 5
01uX-5eC was exposed to red over the entire surface and image formation was performed by line scanning a laser beam in accordance with character signals and image signals, and good prints of both characters and images were obtained.

<Example 27> 3 g of 4-(4-dimethylaminophenyl)-2,6-cyphenylthiapyrylium perchlorate and 5 g of the above-mentioned exemplified charge transport compound (12) were mixed into polyester (Polyester Adhesive 49000, manufactured by DuPont). 100 mj of toluene (50)-dioxane (50) solution! and dispersed in a ball mill for 6 hours. This dispersion was applied onto an aluminum sheet using a Mayer Parr so that the film thickness after drying was 15 μm.

Example 1 The electrophotographic characteristics of the photoreceptor produced in this way
It was measured in the same manner as 0. The results are shown below.

Vo: -698 volts V,: -695 volts E'/2: 1. B iux meeting sec first - Gosho Vo: -697 volts VL: -108 volts 50000' VD Knee 676 volts VL Knee 150 volts <Example 28> An ammonia aqueous solution of casein (casein 1
1.2g, 28% ammonia water 1g, water 222ml
) was coated with Mayer Par and dried to form an adhesive layer with a thickness of 1 μm.

Next, 5 g of a disazo pigment having the following structure and 2 g of butyral resin (degree of butyralization: 63 mol%) were mixed with 9 mol of ethanol.
After being dispersed with a solution dissolved in 5 m It, a charge generation layer having a dry film thickness of 0.4 μm was formed on the adhesive layer.

Next, a charge generation layer was prepared by dissolving 5 g of the above-exemplified charge transport compound (14) and 5 g of poly-4,4'-dioxydiphenyl-2,2-propane carbonate (viscosity average molecular weight 30,000) in 150 mf of dichloromethane. An electrophotographic photoreceptor was prepared by coating and drying on top to form a charge transport layer having a thickness of 11 μm.

The electrophotographic properties of the electrophotographic photoreceptor thus prepared were measured in the same manner as in Example 10. The results are shown below.

Vo: -698 volts V, : -695 volts E'/A: 1.01uxssec Once expanded, V, : -695 volts VL knee 72 volts Vo: -683 volts Vt knee 83 volts <Example 29> One surface is clean The molybdenum plate (substrate) with a thickness of 0.2 mm was fixed at a predetermined position in a glow discharge deposition tank. Next, the inside of the tank was evacuated to a vacuum level of about 5×10-'Torr. Thereafter, the input voltage of the heater was increased to stabilize the molybdenum substrate temperature at 150°C. After that, hydrogen gas and silane gas (15% by volume relative to hydrogen gas) were introduced into the tank.
Adjust the gas flow rate and main valve of the deposition tank to 0.5To.
It was stabilized at rr. Next, 5 MHz high-frequency power was applied to the induction coil to generate glow discharge inside the coil in the tank, resulting in an input power of 30 W.

An amorphous silicon film was grown on the substrate under the above conditions, and the same conditions were maintained until the film thickness reached 2 μm, after which glow discharge was discontinued. After that, turn off the heating heater and high frequency power supply, wait for the substrate temperature to reach 100℃, close the hydrogen gas and silane gas outflow valves, and temporarily drain the inside of the tank for 10-10 minutes.
' After reducing the pressure to below Torr, the pressure was returned to atmospheric pressure and the substrate was taken out. Next, a charge transport layer was formed on this amorphous silicon layer in the same manner as in Example 10 except that the exemplified compound was used as the charge transport compound.

The photoreceptor thus obtained was placed in a charging exposure experimental apparatus, charged with corona at 96 KV, and immediately irradiated with a light image. The light image was illuminated through a transmission type test chart using a tungsten lamp light source. Immediately thereafter, a Φ-charged developer (
A good toner image was obtained on the photoreceptor surface by cascading the toner (containing toner and carrier) onto the photoreceptor surface.

<Example 30> 3 g of 4-(4-dimethylaminophenyl)-2,6-cyphenylthiapyrylium perchlorate and poly(4,4
'-isopropylidene diphenylene carbonate) 3g
After sufficiently dissolving in dichloromethane 200mA, toluene 100mJ! was added to precipitate the eutectic complex. After filtering off this precipitate, dichloromethane was added to redissolve it, and then 100 rrl of n-hexane was added to this solution to obtain a precipitate of a eutectic complex.

5 g of this eutectic complex was added to 95 ml of a methanol solution containing 2 g of polyvinyl butyral, and dispersed in a Pall mill for 6 hours. This dispersion was applied onto an aluminum plate having a casein layer using a Mayer bar so that the film thickness after drying was 0.4 μm to form a charge generation layer.

Next, a coating layer of a charge transport layer was formed on this charge generation layer in exactly the same manner as in Example 10 except that exemplified compound (37) was used.

The electrophotographic properties of the photoreceptor thus prepared were measured in the same manner as in Example 10. The results are shown below.

Vo: -700 volts V, knee 692 volts E! 4: 1.1j! ux*sec May V, : -692 volts VL : -67 volts 50,000 mouths V, knee 690 volts VL knee 82 volts <Example 31> 5 g of the same eutectic complex as used in Example 30 and the above example 5 g of charge transport compound (40) was added to 150 mj of a tetrahydrofuran solution of polyester (Polyester Adhesive 49000, manufactured by DuPont). In addition, the mixture was thoroughly mixed and stirred. This liquid was applied onto an aluminum sheet using a Mayer bar so that the film thickness after drying was 15 μm.

The electrophotographic properties of this photoreceptor were measured in the same manner as in Example 10. The results are shown below.

Vo: -698 volts V, : -695 volts E'74: 1.1 j! uxIIsec expansion
1 VD: -695 volts VL knee 69 volts factory output Vo: -689 volts VL knee 88 volts [Effects of the Invention] As explained above, the novel 5H-dibenzo (a, d) Electrophotographic photoreceptors using cyclohebutanylidene derivatives and 5H-dimenzo (a, d) cyclohebutanylidene derivatives have high sensitivity, and the bright area potential and dark area potential change during continuous image formation by repeated charging and exposure. Accordingly, it is possible to provide an electrophotographic photoreceptor with a small amount of irradiation and excellent durability.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 show infrared absorption spectra by the neat method, and FIGS. 3 to 13 show infrared absorption spectra by the KBr tablet method.

Claims (1)

[Scope of Claims] (1) An electrophotographic photoreceptor characterized by having a layer containing a compound represented by the general formula [I]. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, X is -CH_2CH_2- or -CH=CH-
shows. Further, R^1 and R^2 represent an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group. Further, R^3 and R^4 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. Moreover, Ar_1 represents an aromatic ring group or a heterocyclic group. ] (2) The compound represented by the general formula [I] has the following general formula [
The electrophotographic photoreceptor according to claim 1, which is a compound represented by [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, X, R^1, R^2, R^3, and R^4 have the same meanings as above, and R^6 is a hydrogen atom or an alkyl group. , represents an alkoxy group, a halogen atom or a nitro group. ] (3) The compound represented by the general formula [I] has the following general formula [
The electrophotographic photoreceptor according to claim 1, which is a compound represented by [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] [In the formula, X is -CH_2CH_2- or -CH=CH-
and R^1 and R^2 represent aromatic ring groups. (4) Claim 1, 2 or 3, wherein the layer containing the compound is a charge transport layer of a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer. electrophotographic photoreceptor. (5) A patent in which the layer containing the compound is a charge transport layer of a photosensitive layer having a laminated structure of a charge generation layer and a charge transport layer, and the charge generation layer contains an azo pigment represented by the following general formula: An electrophotographic photoreceptor according to claim 1, 2, or 3. General formula A-(N=N-Cp)_n [In the formula, A is a central skeleton, Cp represents a coupler moiety, and n represents an integer of 2 or 3. ] (6) In the compound represented by the general formula [II], R
^1 and R^3 are ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. The electrophotographic photoreceptor according to claim 2, which is a group selected from the group consisting of ▼ and ▲ which includes mathematical formulas, chemical formulas, tables, etc. (7) In the compound represented by the general formula [III],
R^1 and R^2 are ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc. The electrophotographic photoreceptor according to claim 3, which is a group selected from the group consisting of ▼ and ▲ numerical formula, chemical formula, table, etc. ▼. (8) In the compound represented by the general formula [II], R
^1 and R^2 are CH_3-, C_2H_5-, C
The electrophotographic photoreceptor according to claim 2, which is a group selected from the group consisting of H_3O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼-, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (9) 5H-dibenzo [a,
d] Cycloheptanylidene derivative and 5H-dibenzo [
a, d] cycloheptenylidene derivative. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, X is -CH_2CH_2- or -CH=CH-
shows. Further, R^1 and R^2 represent an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group. Further, R^3 and R^4 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. Moreover, Ar_1 represents an aromatic ring group or a heterocyclic group. ] (10) The 5H-dibenzo[a,d]cycloheptanylidene derivative and 5H according to claim 9, wherein the compound represented by the general formula [I] is represented by the following general formula [II]
-Dibenzo[a,d]cycloheptenylidene derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [In the formula, X, R^1, R^2, R^3 and R^4 have the same meanings as above, and R^5 is a hydrogen atom, an alkyl group, Indicates an alkoxy group, a halogen atom, or a nitro group. ] (11) 5H- according to claim 9, wherein the compound represented by the general formula [I] is represented by the following general formula [III]
Dibenzo[a,d]cycloheptanylidene derivative and 5
H-dibenzo[a,d]cycloheptenylidene derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] [In the formula, X is -CH_2CH_2- or -CH=CH-
and R^1 and R^2 represent aromatic rings. ] (12)
In the compound represented by the general formula [II], R^1 and R^2 are CH_3-, C_2H_5-, ▲ Formula,
5H- according to claim 10, which is a group selected from the group consisting of chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ numerical formulas, chemical formulas, tables, etc. Dibenzo[a,d]cycloheptenylidene derivatives and 5H-dibenzo[a,d]cycloheptenylidene derivatives. (13) In the compound represented by the general formula [II],
R^1 and R^2 are CH_3-, C_2H_5-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
It is a group selected from the group consisting of ▼, which has tables, etc., and ▼, which has mathematical formulas, chemical formulas, tables, etc., and is R^3, R^4
5H-dibenzo[a,d]cycloheptenylidene derivatives and 5H-dibenzo[a,d]cycloheptenylidene derivatives according to claim 10, wherein and R^6 is a hydrogen atom. (14) General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] [In the formula, X is -CH_2CH_2- or -CH=CH-
shows. Further, R^3 and R^4 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. Also, Ar
_1 represents an aromatic ring group or a heterocyclic group. ] and the following general formula [V] R^6-Y[V] [wherein R^6 represents an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group. Moreover, Y represents chlorine, bromine or iodine. ] [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, X is -CH_2CH_2- or -CH=CH-
shows. Further, R^1 and R^2 represent an alkyl group, an aralkyl group, an aromatic ring group or a heterocyclic group. Also, R^3
and R^4 represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. Moreover, Ar_1 represents an aromatic ring group or a heterocyclic group. ] A method for producing a 5H-dibenzo[a,d]cycloheptenylidene derivative and a 5H-dibenzo[a,d]cycloheptenylidene derivative shown in the following. (15) In the compound represented by the general formula [IV] and the general formula [I], Ar_1 is a group represented by ▲a numerical formula, a chemical formula, a table, etc. [a,d]Production method of cycloheptenylidene derivative and 5H-dibenzo[a,d]cycloheptenylidene derivative. [In the formula, R^6 is a hydrogen atom, an alkyl group, an alkoxy group,
Indicates a halogen atom or a nitro group. ] (16) In the compounds represented by the general formula [IV] and the general formula [I], Ar_1 is a group represented by ▲There are numerical formulas, chemical formulas, tables, etc.▼, and R^1 and R^2 are aromatic rings. and 5H-dibenzo[a,d]cycloheptanylidene derivatives and 5H-dibenzo[a,d] according to claim 14, wherein R^3 and R^4 are hydrogen atoms.
]Production method of cycloheptenylidene derivative.