JP3207225B2 - Carbonate resin film and electrophotographic photoreceptor using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbonate resin film and an electrophotographic photosensitive member using the same.

[0002]

2. Description of the Related Art In a conventional organic electrophotographic photosensitive member,
A wet method of forming a photosensitive layer on a substrate using a solvent has been generally used. For example, in a two-layer laminated photoreceptor, an organic pigment having a charge generating function is dispersed and mixed on a substrate together with a binder such as a resin using an organic solvent, and is coated and dried to form a charge generating layer. Next, an organic compound having a charge transfer function is dissolved in an organic solvent together with a binder,
Alternatively, the photoreceptor has been manufactured by dispersing and coating and drying the same to form a charge transfer layer.

[0003] For this reason, there are a number of problems associated with the use of solvents in the wet method. For example, the flammability of solvent vapors,
Problems such as toxicity to the human body and pollution due to emission into the air arise. In addition, there have been serious problems with film formation failure due to sagging and brushing of a coating film at the time of film formation, and manufacturing equipment requiring a large cost.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a deposited film obtained by vacuum deposition in a vacuum apparatus without using an organic solvent, and an organic electrophotographic photosensitive member using the same. .

[0005]

SUMMARY OF THE INVENTION One aspect of the present invention is an A.D. At least one polyhydroxy compound selected from the group consisting of general formulas (1), (2), (3) and (4);
At least one selected from the group represented by general formulas (5) and (6)
Species of carbonate compounds, and optionally C.I. An object of the present invention is to provide a carbonate resin film obtained by subjecting a film obtained by vacuum-depositing a metal acetylacetone compound on a substrate to heat treatment in air or an inert gas, and an electrophotographic photosensitive member using the same.

[0006]

Embedded image (In the formulas (1) to (3), R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, and R ₂ , R ₃ , R
₄ is hydrogen, an alkyl group having 1 to 8 carbon atoms or a phenyl group, m = 1 to 4)

[0007]

Embedded image (In the formula (4), R ¹ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and R ^{2 to} R ⁷ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. )

[0008]

Embedded image (In the formulas (5) and (6), R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, and R ₂ is a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group. Group or tolyl group, m = 1-4)

That is, this carbonate resin film has a property that when a film obtained by vapor-depositing the above specific polyvalent hydroxy compound and a specific carbonate compound on a substrate in vacuum is subjected to heat treatment in the atmosphere, it becomes an extremely hard resinous film. In addition, when the above two compounds are vapor-deposited, if a charge-transporting compound used for a normal organic electrophotographic photoreceptor is vapor-deposited at the same time, the compound is stably taken in and a practical charge-transporting layer can be formed. Was revealed. The present invention has been made based on this fact.

A charge transfer material used in a normal organic electrophotographic photosensitive member, particularly a charge transfer material used in a charge transfer layer of a laminated organic electrophotographic photosensitive member, is vacuum-deposited on the charge generating layer. Even if the charge transfer layer is formed, a photoreceptor having a certain degree of electrical characteristics can be formed. However, in most cases, it could not be used due to the progress of crystallization over time and the occurrence of film peeling. In addition, the mechanical strength of the charge transfer layer was weak, and it could not be used practically from this point. In the present invention, such a problem does not occur at all, since not only the charge transfer material but also the binder material for the charge transfer layer capable of vacuum deposition that does not impair the charge transfer function is simultaneously deposited.

In the present invention, it is also clear that, when the two specific compounds and the charge transfer material are vapor-deposited under vacuum, co-deposition of a compound such as metal acetylacetone also provides better results. Was. Thereby, the photosensitive layer is not melted by the heat treatment, and a film-forming defect does not occur. The charge-transferring material is stably contained in the resinous binder, and a dry film-forming method that does not crystallize for a long time. A charge transfer layer for an organic electrophotographic photoreceptor is obtained.

This dry film forming process does not involve a solvent at all, and the photosensitive member can be manufactured in an extremely clean environment in a vacuum apparatus. Therefore, as in the conventional wet film forming method using a solvent, the whole room is formed in a clean room. And there is an advantage that the equipment cost can be greatly reduced.

Examples of the polyvalent hydroxy compound which can be used in the present invention include the following compounds.

As the divalent hydroxy compound classified into the general formula (1), 2,2-bis- (4-hydroxyphenyl) methane 2,2-bis- (4-hydroxyphenyl) phenylmethane 2,2-bis -(3-chloro-4-hydroxyphenyl) methane 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) phenylmethane 2,2-bis- (4-hydroxyphenyl) ethane 1-phenyl-1 1,1-bis- (4-hydroxyphenyl) ethane 1-phenyl-1,1-bis- (3-methyl-4-hydroxyphenyl) ethane 2,2-bis- (4-hydroxyphenyl) propane 2,2- Bis- (3-methyl-4-hydroxyphenyl) propane 2-methyl-1,1-bis (4-hydroxyphenyl)
Propane 1-ethyl-1,1-bis- (4-hydroxyphenyl) propane 2,2-bis- (3-phenyl-4-hydroxyphenyl) propane 2,2-bis- (2,3,5,6- Tetrafluoro-4
-Hydroxyphenyl) propane 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane 2,2-bis- ( 4-hydroxy-3-isopropylphenyl) propane 2,2-bis- (4-hydroxy-3-secbutylphenyl) propane 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane 2,2 -Bis- (4-hydroxy-3-tert-butylphenyl) propane 2,2-bis- (4-hydroxyphenyl) butane 4-methyl-2,2-bis- (4-hydroxyphenyl) pentane 2, 2-bis- (4-hydroxyphenyl) -4-ethylpentane 2,2-bis- (4-hydroxyphenyl) octane 4,4'-dihi Droxy-2,2,2-triphenylethane and the like.

As the divalent hydroxy compound classified into the general formula (2), 1,1-bis- (4-hydroxyphenyl) cyclohexane 1,1-bis- (4-hydroxy-3-methylphenyl) cyclohexane 1,1 1-bis- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 1,1-bis- (3,5-dichloro-4-hydroxyphenyl) cyclohexane and the like.

The divalent hydroxy compounds classified into the general formula (3) include: {1,1'-bis- (4-hydroxyphenyl) -p-
Diisopropyl benzene 1,1'-bis- (4-hydroxyphenyl) -m-
Diisopropyl benzene and the like.

As the trivalent hydroxy compound classified into the general formula (4), 1,1,1-tris (4-hydroxyphenyl) ethane 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane 1,1,1-tris (4-hydroxy-3,5-dimethylphenyl) ethane 1,1,1-tris (3-chloro-4-hydroxyphenyl) ethane 1,1,1-tris (3,5- Dichloro-4-hydroxyphenyl) ethane 1,1,1-tris (3-bromo-4-hydroxyphenyl) ethane 1,1,1-tris (3,5-dibromo-4-hydroxyphenyl) ethane tris (4- (Hydroxyphenyl) methane tris (4-hydroxy-3-methylphenyl) methane tris (3,5-dimethyl-4-hydroxyphenyl)
Methane tris (3-chloro-4-hydroxyphenyl) methane tris (3,5-dichloro-4-hydroxyphenyl)
Methane tris (3-bromo-4-hydroxyphenyl) methane tris (3,5-dibromo-4-hydroxyphenyl)
Methane and the like.

As the carbonate compounds classified into the general formula (5), 2,2-bis (methylcarbonyldioxy-1,4-phenylene) propane 2,2-bis (ethylcarbonyldioxy-1) , 4-phenylene) propane 2,2-bisdipropylcarbonyldioxy-1,4-
(3-methylphenylene) {propane 2,2-bis} butylcarbonyldioxy-1,4-
(3-methylphenylene) propane 2,2-bis (phenylcarbonyldioxy-1,4-
Phenylene) propane 2,2-bis {phenylcarbonyldioxy-1,4-
(3-methylphenylene) {propane 2,2-bis} phenylcarbonyldioxy-1,4-
(3,5-dimethylphenylene)｝ propane

And carbonate compounds derived from divalent hydroxy compounds classified into the general formula (1) .

As carbonate compounds classified into the general formula (6) , 1,1-bis (phenylcarbonyldioxy-1,4-
Phenylene) cyclohexane 1,1-bis {phenylcarbonyldioxy-1,4-
(3-methylphenylene) {cyclohexane 1,1-bis} phenylcarbonyldioxy-1,4-
(3,5-dimethylphenylene) {cyclohexane 1,1-bis} phenylcarbonyldioxy-1,4-
(3-Chloro-phenylene) cyclohexane A carbonate compound derived from a divalent hydroxy compound classified into the general formula (2) is exemplified.

The method for producing the carbonate compound of the general formula (5) or (6) will be described. Carbonation of these
The compound is a compound of the general formula (1) or (2)
Can be manufactured by the method.

First, the general formula (1) or (2) used in the present invention
A dioxy compound having a cyclohexane ring represented by is a phenol represented by the following formula (7)

[0023]

Embedded image (R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and m is an integer represented by 1 to 4.)

(R ₁ is hydrogen, an alkyl group having 1 to 8 carbon atoms, a halogen atom, and m is an integer represented by 0 to 4.) Ketone of the following formula (8) or (9)

[0025]

Embedded image

Can be produced in a known manner by condensation with Then, these dioxy compounds of the general formula (1) or (2), methyl chloroformate, ethyl chloroformate,
Propyl chloroformate, butyl chloroformate, phenyl chloroformate, chloroformate, etc., in the presence of a base that supplements hydrochloric acid as a reaction product, at a temperature of room temperature to about 100 ° C. The compound of the general formula (5) or (6) can be obtained by reacting in the reaction.

As the hydrochloric acid supplement, triethylamine,
Examples include tributylamine, triallylamine, dimethylaniline, diethylaniline, pyridine, quinoline and the like.

Examples of the solvent include 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran and the like.

The reaction temperature is from room temperature to 100 ° C., preferably from room temperature to 60 ° C., depending on the chloroformate used. The molar ratio of the dioxy compound and phenyl chloroformate of the reacting raw materials is 1: 2 to 1: 4, preferably 1: 2.
2 to 1: 2.3.

[0030]

The metal acetylacetone that can be used in the present invention includes zirconium tetrakisacetylacetone, aluminum trisacetylacetone, zinc acetylacetone, oxytitanium acetylacetone, aluminum tris (ethyl acetate), aluminum tetraisopropylate, aluminum-sec-butylate, and the like. Metal alcoholates such as ethyl acetoacetate aluminum diisopropylate and titanium tetramethoxide. Among these, aluminum tris acetylacetone and aluminum tris (ethyl acetate) are preferred.

A method for producing a carbonate resin film according to the dry method of the present invention will be described. First, to a plurality of evaporation sources of a vacuum evaporation machine, a polyvalent hydroxy compound, a carbonate compound,
And metal acetylacetone. After the substrate is provided on the evaporation source, the inside of the vacuum evaporation machine is evacuated to a degree of vacuum of 10 to ⁵ Torr or less. Next, the evaporation source is heated by a heater to vaporize each raw material and direct a vapor stream to the substrate. The intensity of the vapor flow is controlled by a film thickness monitor provided near the evaporation source so that the vapor deposition ratio of each raw material becomes a predetermined amount.
The deposition ratio of the polyvalent hydroxy compound and the carbonate compound is preferably about 1: 2 to 2: 1 in terms of the molar ratio of the reactive functional groups. If the polyvalent hydroxy compound is large, the film after heating becomes viscous, If the amount is small, it tends to become brittle. The molar ratio of the polyhydroxy compound and the metal acetylacetone is desirably 1: 0.01 to 1: 0.5, preferably about 1: 0.1 to 1: 0.5. Further, it is desirable to provide a shutter between the evaporation source and the substrate in order to control the compounding ratio of these compounds in the deposited film. After a predetermined vapor flow is obtained, the shutter is opened to allow the vapor flow to flow over the substrate to form a vapor deposition film having a desired composition.

The obtained vapor-deposited film is air or nitrogen gas, A
50 to 350 ° C in an inert gas such as r gas, preferably 1 to
At 00 to 200 ° C. for 10 minutes to 10 hours, preferably 30 minutes to 3 hours
Heat treatment for about an hour. This heat treatment is performed after the deposition film is created.
It may be carried out subsequent to the vapor deposition in the vapor deposition machine, or may be once taken out of the vapor deposition machine and subjected to heat treatment by a heater.

By this heat treatment, the deposited film is further stabilized. When heat treatment is performed at a high temperature for a long time, the molecular weight of the deposited film increases, and a strong carbonate resin film can be obtained.

The molecular weight distribution of the film (depending on GPC, polystyrene conversion) tend to usually 10 ⁴ or lower molecular weight component is small is 10 ⁴ or more of the high molecular weight component increases, the latter is increased when the heating temperature increases. Depending on the conditions, the peak value of the molecular weight distribution is about 3 to 5 × 10 ⁴ .

When the heat treatment of the vapor-deposited film is performed under reduced pressure, some components in the vapor-deposited film are re-evaporated and do not have the desired composition. The higher the heating temperature, the stronger this tendency, and the more likely the problem is. Usually about 1 atmosphere or some reduced pressure is preferred.

Further, the higher the heating temperature is, the stronger the film becomes, which is advantageous. However, if the temperature is too high, the film flows and causes problems.

According to the present invention, a compound having photoconductivity can be contained in the above-mentioned carbonate resin film by vapor deposition. That is, in the above-described film forming process, a single layer type or a laminated type electrophotographic photoreceptor can be easily formed by further providing an evaporation source in the vacuum deposition machine so that the charge transfer material and the charge generation material can be deposited. Can be manufactured.

In a single-layer type electrophotographic photoreceptor, at least five or more kinds of raw materials may be co-deposited. In a stacked type electrophotographic photoreceptor, a charge generation material may be deposited on a substrate to form a charge generation layer, and then a material for forming a charge transfer layer may be deposited to form a charge transfer layer. What is necessary is just to reverse this procedure for a reverse layer structure. Thus, the layer configuration can be easily selected only by changing the order of these film forming processes.

The composition distribution and concentration of the charge generation material, the charge transfer material and other materials in the photosensitive layer can be controlled by monitoring the vapor flow during vapor deposition and controlling the intensity thereof, or by opening and closing a shutter. You can control the distribution. In particular, in a laminated photoreceptor, increasing the concentration of the charge transfer material at the interface between the charge generation layer and the charge transfer layer has a favorable effect on sensitivity and the like. Further, in a photoreceptor having a two-layer type photosensitive layer, the surface strength can be increased by decreasing the concentration of the charge transfer material on the surface side. Such a method is a feature of the dry film forming method. As the charge transfer material and charge generation material for an organic electrophotographic photosensitive member that can be used in the present invention, known materials can be used. Any material that can be vacuum-deposited is applicable to this dry-type film forming process.

Examples of usable charge generating materials include amorphous selenium, halogen-doped amorphous selenium; selenium-based photoconductive materials such as selenium arsenide, selenium tellurium, antimony selenium arsenide, and halogen-pselenium alloy; and amorphous silicon. ,
Examples include amorphous silicon-based photoconductive materials such as hydrogen or halogen doped amorphous silicon, nitrogen or carbon containing amorphous silicon, and hydrogen or halogen doped nitrogen or carbon containing amorphous silicon. Metal-free phthalocyanine; metal phthalocyanine pigments such as copper phthalocyanine and titanyl phthalocyanine; perylene pigments; quinacridone pigments such as monastral violet (manufactured by DuPont); polycyclic quinone pigments;

As the charge transfer material, conventionally known electron accepting compounds and electron donating compounds can be used. Examples of the electron accepting compound include fluorenone compounds such as tetracyanoethylene and 2,4,7-trinitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, and 2,4,8-thioxanthone. Nitro compounds such as 3,4,5,7-tetranitro-9-fluorenone, 3,5-dimethyl-3 ', 5'-
Di-tert-butyldiphenoquinone, 3,3 ′, 5
Diphenoquinone compounds such as 5'-di-tert-butyl diphenoquinone;

Examples of the electron donating compound include N, N-diethylaminobenzaldehyde-N, N-diphenylhydrazone, N-methyl-3-carbazolylaldehyde.
Hydrazone compounds such as N, N-diphenylhydrazone,
2,5-di (4-N, N-dimethylaminophenyl)-
1,3,4-oxadiazol, 2,5-di (4-N,
Oxadiazol compounds such as N-diethylaminophenyl) -1,3,4-oxadiazol, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as N-ethylcarbazole, 1-phenyl-3- (4-dimethylaminophenyl) pyrazoline, 1-phenyl-3- (4-dimethylaminostyryl) -5- (4-dimethylaminophenyl)
Pyrazoline compounds such as pyrazoline and 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazolin; 2- (4-diethylaminophenyl) -4- (dimethylaminophenyl) -5
Oxazo- such as-(2-chlorophenyl) oxazole
Compounds, isoxazole compounds, thiazole compounds such as 2- (4-diethylaminostyryl) -6-diethylaminobenzothiazol, triphenylamine, 4,4'-bis {N- (3 -Methylphenyl) -N
Amino derivatives such as phenylamino dibiphenyl, stilbene compounds, thiadiazole compounds, imidazo-
And nitrogen-containing cyclic compounds such as pyrazole-based compounds, indole-based compounds and triazole-based compounds, and condensed polycyclic compounds such as anthracene, pyrene and phenanthrene.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0045]

【Example】

(Synthesis Example 1) 1,1-bis (phenylcarbonyldioxy-1,4-
Synthesis Example of (phenylene) cyclohexane 26.8 g of 1,1-bis (4-hydroxyphenyl) -cyclohexane was taken in 300 ml of dry dioxane, and 24.3 g of triethylamine was added and dissolved. To this, 36.3 g of phenyl chloroformate was diluted with 100 g of dry dioxane, and the reaction solution was added from room temperature to 50 ° C. over 1 hour. Then 60 ° C
After stirring for 2 hours, the reaction solution was poured into 800 ml of water.
After standing for 1 day, the precipitated oily substance was collected, poured into a mixed solution of 500 ml of water and 100 ml of toluene, mixed and stirred, and separated by a separating funnel to obtain a colorless transparent solution. After repeating this operation several times and washing well, the solvent was separated to obtain 51.0 g of an oily substance.
Hexane (150 ml) was added thereto, followed by stirring to precipitate white crystals and dried. This crude crystal was recrystallized with hexane to obtain 45.2
g of a white powder was obtained.

Mp 87-88 ° C. Elemental analysis value (%) Actual measurement value (calculated value) C: 75.79 H: 5.40 (75.56) (5.56) IR spectrum (KBr tablet method) is shown in FIG.

Synthesis Example 2 2,2-Bis (phenylcarbonyldioxy-1,4-
Synthesis example of phenylene) propane 2,2-bis (4-hydroxyphenyl) propane 15.7
g in 300 ml of dry dioxane and triethylamine 26.0
g was added and dissolved. Dilute 33.0 g of phenyl chloroformate in 100 g of dry dioxane and bring the reaction solution from room temperature to 50 ° C.
Was added over 1 hour while maintaining the temperature. After stirring at 60 ° C. for 2 hours, 100 ml of water was added to the reaction solution. 1
After standing for a day, the precipitated white substance was collected, poured into a mixed solution of 300 ml of water and 200 ml of toluene, mixed and stirred, and separated.
And a colorless transparent solution was obtained. After repeating this washing operation several times, the solvent was separated to obtain 30.4 g of crude crystals. This crude crystal was recrystallized with cyclohexane to obtain 25.2 g.
Was obtained as a white powder.

Mp 103-103.5 ° C. Elemental analysis value (%) Actual measurement value (calculated value) C: 74.46 H: 5.04 (74.35) (5.16) Example 1 The two evaporation sources in the vacuum evaporation apparatus were 2,2- Screw (4-
25 g of hydroxyphenyl) propane and 50 g of 2,2-bis (phenylcarbonyldioxy-1,4-phenylene) propane were separately charged. The glass plate was attached to the substrate holder, and the vacuum was evacuated to a vacuum of 10 to ⁵ Torr or less using a vacuum pump.

Next, the evaporation source was heated to control the temperature, and the deposition ratio was set to 1: 1 in terms of mol ratio by a film thickness monitor.
The shutter was opened and co-evaporation was performed for 30 minutes. The obtained co-evaporated film was subjected to a heat treatment at 180 ° C. for 2 hours in the atmosphere to obtain a colorless and transparent resinous film.

The IR spectrum of this resinous film (KBr
Method) was very close to commercially available polycarbonate (FIGS. 2, 3). The number average molecular weight by GPC was about 10 ⁴ .

Example 2 In Example 1, one more evaporation source was added.
2.5 g of l-acetylacetone was charged and co-evaporated. The deposition ratio was 2,1: bis (4-hydroxyphenyl) propane, 2,2-bis (phenylcarbonyldioxy-1,4-phenylene) propane and Al acetylacetone in a molar ratio of 1: 1: 0.1. is there. Next, the co-deposited film was heated at 150 ° C. for 1 hour in the atmosphere to obtain a colorless, transparent and highly smooth resinous film.

Example 3 In Example 2, 1,1 was used as the divalent hydroxy compound.
Resin-like films were prepared in the same manner except that -bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane were used as carbonate compounds. This film was also a colorless, transparent and highly smooth resinous film.

Example 4 In Example 2, as a divalent hydroxy compound, $ 1,
1'-bis- (4-hydroxyphenyl) -p-diisopropyl @ benzene, 1,1 as a carbonate compound
A resinous film was prepared in the same manner except that -bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane was used. This film was also a colorless, transparent and highly smooth resinous film.

Example 5 In Example 2, 2,2 was used as the divalent hydroxy compound.
-Bis- (3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) as a carbonate compound
A resinous film was prepared in the same manner except that cyclohexane was used. This film was also a colorless, transparent and highly smooth resinous film.

Example 6 In Example 2, 1,3 was used as the trivalent hydroxy compound.
A resinous film was prepared in the same manner except that 1,1-tris (4-hydroxyphenyl) ethane and 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane were used as a carbonate compound. This film was also a colorless, transparent and highly smooth resinous film.

Example 7 Predetermined amounts of the following five compounds were separately charged into five evaporation sources in a vacuum evaporation apparatus.

1) 1,1-bis (4-hydroxyphenyl) cyclohexane 2) 1,1-bis (phenylcarbonyldioxy-1,4
-Phenylene) cyclohexane 3) Al acetylacetone 4) 4'-N, N-bis (4-methylphenyl) amino-
Install the α- -phenylstilbene 5) titanyl phthalocyanine Al plate on a substrate holder, 10 ~ ⁵ the To with a vacuum pump
It was evacuated to a vacuum of rr or less.

Next, the evaporation source was heated to control the temperature, and the evaporation ratio was 1: 2: 0.1:
After 3: 3, the shutter was opened and co-evaporation was performed for 60 minutes. The obtained co-deposited film was subjected to a heat treatment at 150 ° C. for 2 hours in the atmosphere to obtain a single-layer electrophotographic photosensitive member. The film thickness was 11 microns. This photoreceptor was mounted on an Al drum and attached to a printer for writing with a laser light source, and when printed out, a clear image with no point defects was obtained.

Example 8 Titanyl phthalocyanine was vacuum-deposited on an Al plate by another vapor deposition machine to form a 1500 A charge generation layer. Example 7
Was attached to the substrate holder of the vapor deposition machine. Next, a 13-micron charge transfer layer was formed by vapor deposition in the same manner as in Example 7 except that the evaporation source of 5) in Example 7 was not used to obtain a two-layer type electrophotographic photosensitive member. This photoreceptor was mounted on an Al drum and attached to a printer for writing with a laser light source, and when printed out, a clear image was obtained.

Example 9 A vacuum evaporation machine similar to that of Example 7 was prepared except that the evaporation source of Example 7 was not provided and the four evaporation sources were provided. Other than that, only the charge transfer layer was formed in the same manner as in Example 7. The film thickness was 13 microns.

On this charge transfer layer, a charge generation layer of titanyl phthalocyanine of 2000 ° was formed by vacuum evaporation.
Heat treatment was performed at 150 ° C. for 20 minutes in a nitrogen gas to obtain a two-layer type electrophotographic photosensitive member. This photoreceptor was mounted on an Al drum, and the mounted image was copied on a positive charging type copying machine using a halogen lamp as a light source. A clear image was obtained.

Example 10 A two-layer type photoreceptor was prepared using only the vacuum evaporation machine of Example 7. That is, first, co-evaporation is performed for 45 minutes using only the evaporation source from 1) to 4), and subsequently, the shutter of the evaporation source of 5) is also opened and co-evaporation is performed for 15 minutes, and titanyl phthalocyanine is formed on the upper part of the charge transfer layer. A two-layer type electrophotographic photosensitive member was prepared. This was heat-treated at 150 ° C. for 20 minutes in the atmosphere. This photoreceptor was mounted on an Al drum, and the mounted image was copied on a positive charging type copying machine using a halogen lamp as a light source. A clear image was obtained.

Example 11 Metal-free phthalocyanine was vacuum-deposited on an Al plate by another vapor deposition machine to form a charge generating layer of 2000 °. This was attached to the substrate holder of the vapor deposition machine of Example 7. Next, in Example 7, 4′-N, which is the electron donating compound of 4),
N-bis (4-methylphenyl) amino-α-phenylstilbene is changed to 3,5-dimethyl-3 ′, 5′-ditertbutyldiphenoquinone, which is an electron accepting compound, and 5) the evaporation source is used. A two-layer type electrophotographic photoreceptor was obtained in the same manner as in Example 7 except that the electrophotographic photoreceptor was not used. The film thickness was 15 microns. This photoreceptor was attached to an Al drum and mounted on a positive charging type copying machine using a halogen lamp as a light source. The image was copied, and a clear image was obtained.

Example 12 The two-layer type photosensitive member for positive charging in Example 9 was attached to a vacuum evaporation machine having the following three evaporation sources.

1) 2,2-bis (4-hydroxyphenyl) propane 2) 2,2-bis (phenylcarbonyldioxy-1,4
-Phenylene) propane 3) 3,5-dimethyl-3 ', 5'-ditertbutyldiphenoquinone Vacuum is drawn to a vacuum of 10 to ⁵ Torr or less using a vacuum pump, and then the evaporation source is heated to control the temperature. After the deposition ratio was 1: 2: 3 by weight on the film thickness monitor, the shutter was opened and co-deposition was performed for 60 minutes. The obtained co-deposited film was heated at 130 ° C. for 2 hours in a nitrogen gas at 1 atm to obtain a three-layer type electrophotographic photosensitive member. The overall film thickness was 21 microns.
This photoreceptor was attached to an Al drum and attached to a positive charging type copying machine having a halogen lamp as a light source. When the image was copied, a clear image having no point defects was obtained.

[0066]

According to the dry film forming process of the present invention, an organic electrophotographic photosensitive member can be manufactured in a vacuum apparatus without involvement of a solvent, so that the problem of using a solvent can be avoided and a space having a very high degree of cleanness can be obtained. Thus, a high-performance electrophotographic photosensitive member having no point defects can be provided.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane obtained in a synthesis example.

FIG. 2 shows the IR of the carbonate resin film obtained in Example 1.
Spectrum.

FIG. 3 is an IR spectrum of a commercially available carbonate resin film.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03G 5/05 101 G03G 5/05 101 (72) Inventor Shinichi Nomura 1-3-1 Eda Nishi Midori-ku, Yokohama-shi, Kanagawa Pref. Stanley Inside Electric Co., Ltd. (72) Inventor Fumiyuki Suda 1-3-1 Edanishi, Midori-ku, Yokohama, Kanagawa Prefecture Inside Stanley Electric Co., Ltd. (72) Inventor Satoshi 1-3-3, Edanishi, Midori-ku, Yokohama, Kanagawa 1 Stanley Electric Co., Ltd. (72) Inventor Yoichi Fukuda 1-3-1 Edanishi Midori-ku, Yokohama-shi, Kanagawa Prefecture Stanley Electric Co., Ltd. (56) References JP-A-2-269358 (JP, A) Kaihei 4-234763 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23C 14/12 C08G 63/00-64/42 G03G 5/00-5/16 CA (STN)

Claims (4)

(57) [Claims] 1. An A.I. At least one polyvalent hydroxy compound selected from the group represented by the following general formulas (1) to (4); At least one carbonate compound selected from the group represented by the following general formulas (5) and (6); A carbonate resin film obtained by subjecting a film obtained by vacuum-depositing a metal acetylacetone compound on a substrate to heat treatment in air or an inert gas. Embedded image (In the formulas (1) to (3), R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, and R ₂ , R ₃ , R
₄ is hydrogen, an alkyl group having 1 to 8 carbon atoms or a phenyl group, m = 1 to 4) (In the formula (4), R ¹ is hydrogen, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and R ^{2 to} R ⁷ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ) (In the formulas (5) and (6), R ₁ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a halogen atom, and R ₂ is a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group. Group or tolyl group, m = 1-4) 2. The carbonate resin film according to claim 1, wherein the metal acetylacetone compound is Al trisacetylacetone or Al tris (ethyl acetate). 3. An electrophotographic photoreceptor obtained by simultaneously depositing a compound having photoconductivity in the carbonate resinous film according to claim 1 or by subjecting it to a subsequent heat treatment. 4. A multilayer comprising a resin film according to claim 1, wherein a charge transfer layer containing an electron donating compound and / or an electron withdrawing compound is formed adjacent to the charge generating layer. Type electrophotographic photoreceptor.