JP3234332B2 - Electrophotographic photoreceptor and method of manufacturing 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 an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic photosensitive member containing a photoconductive polymer compound as a charge transporting substance.

[0002]

2. Description of the Related Art Conventionally, electrophotographic copying machines and printers using the Carlson process have been used for their printing quality, speed,
It has been widely adopted because of its good operability. In recent years, photoconductors mounted on these electrophotographic devices have become mass-produced, pollution-free,
And an organic electrophotographic photosensitive member having excellent sensitivity characteristics. However, this organic electrophotographic photoreceptor still has some problems that have to be solved in terms of characteristics as compared with a photoreceptor in which a conventionally used inorganic material is provided in a photosensitive layer.

[0003] Among them, improvement of durability against abrasion,
Improvement of mechanical strength against scratches, scratches, peels, etc.,
There is an urgent need to improve the deterioration of the characteristics of the photoconductor when a liquid developer is used in place of the dry developer. Organic electrophotographic photoreceptors often employ a configuration in which a charge generation layer and a charge transfer layer are sequentially stacked from a conductive support substrate in order to increase sensitivity and protect the charge generation layer. Normal,
As the charge transfer layer of the layered organic electrophotographic photoreceptor, a charge transfer layer obtained by dispersing and dissolving a low-molecular charge transfer material in a resin and coating the resin by a method such as dipping is used. As the resin having the binder function, polycarbonate, polyester, polymethyl methacrylate and the like are used, but the binder resin itself is made of an electrically inactive polymer, and has the charge transfer performance as described above. When the substance is contained in an amount of about 40 to 60 wt%, the polymer binder is electrically activated, and a practical charge transfer layer can be obtained.

[0004] In this way, a charge transfer layer that is electrically satisfactory can be obtained, but it has been known that the inherent properties of the binder resin are reduced due to the large content of the charge transfer substance. Although some measures have been taken in the electrophotographic process for this purpose, abrasion, scratches, cracks and the like of the photosensitive layer have become a serious problem with the recent increase in copy cycles.

When a liquid developer is used in an electrophotographic process, the photosensitive layer comes into contact with a carrier liquid such as isoparaffin, causing various problems. For example, elution of low-molecular compounds, crystallization, phase separation, etc. occur, and the basic function of the photosensitive layer deteriorates. To solve this problem, it has been proposed to provide a protective layer or the like made of amorphous carbon or a metal oxide thin film or a resin film in which the metal oxide is dispersed, which can provide mechanical strength. Has not been reached.

As a proposal for solving these problems, a photoreceptor containing a polyarylamine compound (JP-A-64-996)
4) A photoreceptor containing a hydroxyarylamine compound (JP-A-1-105260) has also been proposed. The former is a polycarbonate copolymer exhibiting charge transport ability in which triphenylamine structural units having charge transport ability between carbonate bonds and oxyalkylene structural units providing a flexible structure during film formation are alternately provided. However, although this copolymer is rich in flexibility, it has poor mechanical strength and is insufficient as an improvement method. In the latter case, a charge transfer layer in which a low molecular charge transfer material having a plurality of hydroxyl groups introduced into a triphenylamine structure is contained in a polar resin binder is provided on the photoreceptor. However, this photosensitive member was brought into contact with a solvent of a liquid developer to obtain a good result, but the mechanical strength was similarly poor and was insufficient as an improvement method.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve these problems and to provide an organic electrophotographic photosensitive member having high mechanical strength and excellent solvent resistance.

[0008]

According to the present invention, in an electrophotographic photosensitive member having an organic photosensitive layer provided on a support, the photosensitive layer is a polymer having an arylamine structural unit,
This is achieved by the polymer containing a polymer having a molecular structure three-dimensionalized by a carbonate bond.

The polymer having a three-dimensional arylamine structural unit according to the present invention is roughly represented by the general formulas (I) to (III), wherein ━ represents a carbonate bond, and part or all of the charge transfer layer. Contains a three-dimensional structure. A represents an arylamine group, and B and C represent a substituted or unsubstituted aromatic group.

[0010]

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A: an arylamine group having 2 or more valences 3 B: an aromatic or substituted aromatic group having 2 or more valences C: an aromatic or substituted aromatic group having 2 or more valences 1: an integer of 1 or more m: an integer of 0 or more n: an integer of 0 or more Also, A, B, and C may all be trivalent or more groups at the same time, but at least one is a trivalent or more group. The above A, B and C are arranged alternately or randomly. These three structural units are represented by the following formulas (IV) to
It is preferable to satisfy (VI).

[0012]

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Usually, the ratio of l, m and n is selected so as to satisfy the electrical characteristics, mechanical characteristics and solvent durability within this range. In a preferred example, when A and B are divalent and C is trivalent, the ratio of l is 0.50 to 0.7 and the ratio of n is 0.20 to 0.20.
The ratio of 0.30, m is the remainder. When A is trivalent and C is divalent without using B, the ratio of l is 0.50 to 0.7 and the ratio of n is 0.30 to 0.50. It is preferred that the ratio of at least trivalent groups is 0.20 or more. When the usage ratio of the trivalent group is less than 0.20, the solvent durability decreases. The ratio of A having an arylamine structure is 0.4
If it is less than 0, it is not preferable in terms of electrical characteristics.

The polymer can be produced by oligomerizing the following monomers to a molecular weight of 1 × 10 ⁴ or less by a known method, followed by polymerization. As a method for obtaining an oligomer having a carbonate bond from the monomer according to the present invention, there are a phosgene method and a transesterification method, and a transesterification method using no highly toxic phosgene is preferable.

In order to form the charge transfer layer of the present invention having a three-dimensional structure by combining the obtained oligomers and monomers, a transesterification method is preferred. The manufacturing method will be described below. As the hydroxyarylamine compound in the present invention, a compound into which a plurality of hydroxyl groups are introduced, which is suitable for the present invention, can be synthesized by applying or applying a known method. For example, the following compounds may be mentioned.

[0016]

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The polyhydroxy compounds having no triphenylamine structure which can be used in the present invention include, as typical examples, compounds represented by the following general formulas (1) to (4). The compound having a plurality of hydroxyl groups applicable to the present invention is not limited to these.

[0018]

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[In the formulas (1) to (3), R ₀ is hydrogen or an alkyl group having 1 to 4 carbon atoms containing a straight or branched chain, a phenyl group, a halogen atom, and m = 1 to 4. R ₁ , R ₂ ,
R ₃ is hydrogen, a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group. ]

[0020]

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[In the formula (4), R ₁ is hydrogen or a compound having 1 to 1 carbon atoms.
5 is an alkyl group and a phenyl group, and R _{2 to} R ₇ are each hydrogen or an alkyl group having 1 to 4 carbon atoms or a halogen atom. Examples of the hydroxy compound that 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-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-sec Butylphenyl) 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′-dihydroxy-2,2,2-
Triphenylethane and the like.

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

As the divalent hydroxy compound classified into the general formula (3), [1,1'-bis- (4-hydroxyphenyl) -p-diisopropyl] benzene, [1,1 '
-Bis- (4-hydroxyphenyl) -m-diisopropyl] benzene and the like.

The trivalent hydroxy compounds classified into the general formula (4) include 1,1,1-tris (4-hydroxyphenyl) ethane and 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.

The carbonate compound usable in the present invention includes a carbonate compound derived from a compound having a plurality of hydroxyl groups. More preferably, compounds represented by the following general formulas (5) to (8) are exemplified.

[0027]

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[0028] wherein (5) ~ (7), R 0 is an alkyl group, a phenyl group containing a linear or branched C1-4 hydrogen or carbon is m = 1 to 4 halogen atoms, R ₁ To R ₃ are an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a tolyl group. ]

[0029]

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[In the formula (8), R ₁ is hydrogen or C ₁ -C 1
5 is an alkyl group and a phenyl group, and R _{2 to} R ₇ are each hydrogen or an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ₈ is an alkyl group having 1 to 4 carbon atoms, a tolyl group, or a phenyl group. As carbonate compounds classified into the general formula (5), 2,2-bis (methylcarbonyldioxy-1,4-phenylene) propane,
2-bis (ethylcarbonyldioxy-1,4-phenylene) propane, 2,2-bis [propylcarbonyldioxy-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.

The carbonate compounds classified into the general formula (6) include 1,1-bis (methylcarbonyldioxy-1,4-phenylene) cyclohexane and 1,1-bis (ethylcarbonyldioxy-1,4- (Phenylene) cyclohexane, 1,1-bis (butylcarbonyldioxy-1,4-phenylene) cyclohexane, 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane, 1,1-bis [phenylcarbonyl Dioxy-1,4- (3-methylphenylene)] cyclohexane, 1,1-bis [phenylcarbonyldioxy-1,4- (3,5-dimethylphenylene)] cyclohexane, 1,1-bis [phenylcarbonyl Dioxy-1,4- (3-chloro-phenylene)] cyclohexane.

The compounds classified into the general formulas (7) and (8) include [1,1′-bis- (methylcarbonyldioxy-1,4-phenylene) -p-diisopropyl] benzene, 1'-bis- (phenylcarbonyldioxy-1,4-phenylene) -m-diisopropyl] benzene, 1,1,1-tris (methylcarbonyldioxy-1,4-phenylene) ethane, 1,1,1 -Tris (phenylcarbonyldioxy-1,4-phenylene)
Ethane.

A method for producing a carbonate compound of the general formula (6) from a compound of the general formula (2) will be described. Other carbonate compounds can be produced in the same manner. First, a dioxy compound having a cyclohexane ring represented by the general formula (2) is a phenol represented by the following general formula (9).

[0034]

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(R ₀ is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, a phenyl group, a halogen atom,
m is an integer represented by 1-4. ) Ketone of the following formula (10)

[0036]

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It can be produced in a known manner by condensation with

Next, the obtained dioxy compound having a cyclohexane ring of the formula (2) and a chloroformate such as methyl chloroformate, ethyl chloroformate, propyl chloroformate, butyl chloroformate, phenyl chloroformate and the like. The compound of the formula (6) can be obtained by reacting the compound with a compound in a suitable solvent at a temperature of about room temperature to about 100 ° C. in the presence of a base that supplements hydrochloric acid as a reaction product. it can.

As a hydrochloric acid supplement, triethylamine,
Examples include tributylamine, triallylamine, dimethylaniline, diethylaniline, pyridine, quinoline and the like. Further, as the solvent, 1,2-methoxyethane, 1,1,
2-ethoxyethane, bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran and the like can be mentioned.

The reaction temperature depends on the chloroformate to be used, but it is from room temperature to 100 ° C., preferably from room temperature to 60 ° C.
It is. The molar ratio between the reacting dioxy compound and the chloroformate is usually from 1: 2 to 1: 4, preferably from 1: 2.
2.2 to 1: 2.3. The synthesis examples of typical monomers and oligomers of the present invention are shown below.

(Synthesis Example 1): Synthesis of Monomer N, N'-diphenyl-N, N'-bis (3-hydroxyphenyl)-[1,1'-biphenyl] -4,4'-
Synthesis of Diamine (Exemplified Compound A-2) According to Example 1 of Showa 64-9964,
20 g of N, N′-diphenyl-N, N′-bis (3-methoxyphenyl)-[1,1′-biphenyl] -4,4′-diamine and 32.5 g of NaI were added to hot sulfolane 10
After heating to 120 to 180 ° C. in 0 cc, maintaining at 60 ° C., sequentially adding 5 cc of water and 27.7 g of trimethylchlorosilane, and hydrolyzing the compound to give Exemplified Compound A-
Compound 2 was synthesized. Then, the product was purified by a conventional method and dried to obtain 5.6 g of an off-white powder.

Mp 227-228 ° C. Elemental analysis value (%) Actual value (calculated value) C: 83.05 (83.10) H: 5.54 (5.42) N: 5.07 (5.38) (Synthesis Example 2): Synthesis of Monomer 1,1-bis (phenylcarbonyldioxy-1,4-
Synthesis of phenylene) cyclohexane 16.8 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 kept at room temperature to 50 ° C. and added over 1 hour. Then, after stirring at 60 ° C. for 2 hours, the reaction solution was poured into 800 ml of water. After standing for one 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 washing operation several times, the solvent was separated to obtain 51.0 g of an oily substance. Hexane (150 ml) was added thereto, mixed and stirred to precipitate white crystals, which were dried. The crude crystals were recrystallized from hexane to give 45.2 g.
Was obtained as a white powder.

Mp 87-88 ° C. Elemental analysis value (%) Actual measurement value (calculated value) C: 75.79 (75.56) H: 5.40 (5.56) (Synthesis example 3): Synthesis of monomer 2 , 2-Bis (phenylcarbonyldioxy-1,4-
Synthesis example of phenylene) propane 2,2-bis (4-hydroxyphenyl) propane 1
5.7 g was taken in 300 ml of dry dioxane, and 26.0 g of triethylamine was added and dissolved. To this, 33.0 g of phenyl chloroformate was diluted with 100 g of dry dioxane, and added over 1 hour while keeping the reaction solution at room temperature to 50 ° C. Then, after stirring at 60 ° C. for 2 hours,
100 ml of water was added to the reaction solution. After standing for one 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 by a separating funnel to obtain a colorless transparent solution. After repeating this washing operation several times,
The solvent was separated to obtain 30.4 g of crude crystals. The crude crystals were recrystallized from cyclohexane to obtain 25.2 g of a white powder.

Mp 103-103.5 ° C. Elemental analysis value (%) Actual value (calculated value) C: 74.46 (74.35) H: 5.04 (5.16) In the present invention, the hydroxyarylamine compound And an oligomer is produced using a monomer of a hydroxy compound and a carbonate compound containing at least one kind of trifunctional compound represented by the general formulas (1) to (8). As a specific method, a production method using a transesterification method will be described.
A typical example of the synthesis of an oligomer having a triphenylarylamine structure is shown below.

(Synthesis example 4): Synthesis of oligomer Exemplary compound A-2, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1,1-tris (phenylcarbonyldioxy-1,4-phenylene) Ethane was mixed at a molar ratio of 3: 0.5: 2 and charged into a flask equipped with a stirrer.

The temperature was raised from room temperature to 230 ° C. over 1 hour while flowing dry nitrogen gas, and this temperature was maintained for 2 hours. Then, the pressure was reduced by a vacuum pump and the pressure was reduced to 2 at 10 Torr.
It was kept at 50 ° C. for 1 hour. At this time, release of a large amount of phenol was confirmed. This was naturally cooled to room temperature to obtain a viscous product.

The product was washed with methyl ethyl ketone and filtered to obtain a white powder. This was dissolved in a small amount of methanol, reprecipitated and purified, and the molecular weight distribution was examined.
No more than 00 oligomers were included. In the IR spectrum of the product, absorption bands at 3300 to 4000 cm ^-1 due to hydroxyl groups were observed.

(Synthesis Example 5) Synthesis of Oligomers Exemplified Compound A-2, 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane,
1,1-tris (phenylcarbonyldioxy-1,4
-Phenylene) ethane was mixed in a molar ratio of 5: 1: 4 in the same manner as in Synthesis Example 3 except that the molecular weight was 300.
0 or less oligomer was obtained.

(Synthesis Example 6) Synthesis of Oligomers Exemplified Compound A-2 and 2,2-bis (phenylcarbonyldioxy-1,4-phenylene) propane were mixed at a molar ratio of 1: 2. Except for the above, an oligomer having a molecular weight of 6000 or less was obtained in the same manner as in Synthesis Example 3. In this case, the IR spectrum shows a hydroxyl group of 3300 to 4000 cm.
^No absorption band of ^-1 was observed. As can be seen from the above Synthesis Examples 4 to 6, the terminal group of the oligomer can be substantially controlled by the molar ratio of the carbonate compound and the hydroxy compound.

Then, these oligomers are dissolved and diluted with an appropriate solvent, coated, dried and cured to obtain the photosensitive layer of the present invention. One oligomer and one monomer in combination, or two or more oligomers,
Alternatively, two or more kinds of oligomers and one kind of monomer can be used. In this case, it is preferable that the equivalent of the functional group to be transesterified is satisfied.

The drying and curing temperature of the photosensitive layer is usually from 150 to 30.
The temperature is 0 ° C, preferably 180 to 250 ° C, for 30 minutes to 24 hours, preferably 1 hour to 5 hours. Higher temperatures cure faster. In particular, at high temperatures, the photosensitive layer may be deteriorated along with the curing due to the influence of oxygen in the atmosphere.
In order to prevent this, it is preferable to cure in an inert gas such as dry nitrogen gas or argon.

A known compound may be used as a curing accelerator. Particularly preferred compounds include the following metal acetylacetones and organic metal salts. For example, zirconium tetrakisacetylacetone, aluminum trisacetylacetone, zinc acetylacetone, oxytitanium acetylacetone, aluminum tris (ethyl acetate).

Further, metal alcoholates such as aluminum tetraisopropylate, aluminum sec-butylate, ethyl acetoacetate aluminum diisopropylate, titanium tetramethoxide and the like can be mentioned. Among these, aluminum tris acetylacetone and aluminum tris (ethyl acetate) are preferred.

These compounds are added to the coating solution for forming the charge transfer layer of the present invention. The amount of addition is 0.01 to 20% by weight or less based on the solid content of the coating solution. The smaller the amount, the better, and the maximum, the addition is made within the range not affected by the characteristics of the photoreceptor.

The electrophotographic photoreceptor of the present invention may be used in a form in which a charge transfer layer is laminated on a charge generation layer, or in a form in which a charge transfer layer is laminated on a charge transfer layer. Alternatively, a charge generating material may be dispersed and contained in the charge transfer layer of the present invention to be used as a single layer type photoreceptor. or,
A protective layer having a suitable light-transmitting resistance may be laminated for surface protection. Alternatively, an adhesive layer or a charge injection preventing layer may be provided between the support having a conductive surface and the photosensitive layer.

As the conductive support which can be used for the electrophotographic photosensitive member of the present invention, a known support can be used. For example, a metal such as aluminum, nickel, copper, nichrome, or a plastic film such as polyethylene terephthalate, or a metal such as aluminum, platinum, or palladium, or a conductive metal oxide may be subjected to conductive treatment by a method such as vapor deposition or sputtering. There is a flexible support.

Examples of usable charge generation materials include amorphous selenium, halogen-doped amorphous selenium; selenium-based photoconductive materials such as selenium arsenide, selenium tellurium, antimony selenium arsenide, and halogen-doped selenium alloy;
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 amorphous silicon containing nitrogen or carbon. Known materials such as metal-free phthalocyanine; metal phthalocyanine pigments such as copper phthalocyanine and titanyl phthalocyanine; azo pigments; perylene pigments; quinacridone pigments such as monastral violet (manufactured by DuPont); and polycyclic quinone pigments can be used. When an organic pigment is used for the charge generation layer, it is dispersed and applied together with a binder resin. There is no particular limitation on the resin that can be used,
Examples include butyral resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride, polyurethane, epoxy resin, polyamide, polycarbonate, polyester, acrylic resin, alkyd resin and the like. Further, the oligomer or polymer of the present invention may be contained, or a charge transfer material described later may be added for improving the properties.

As the charge transfer layer, in addition to using the polymer of the present invention, known polycarbonates can be used in combination for improving performance. Alternatively, a known charge transfer material can be used in addition to the polymer of the present invention. This is particularly effective when the photosensitive layer requires mechanical strength rather than solvent durability, or for improving electrical characteristics. As the charge transfer material,
Conventionally known electron accepting compounds and electron donating compounds can be used together.

Examples of the electron accepting compound include fluorenone compounds such as tetracyanoethylene, 2,4,7-trinitro-9-fluorenone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, 2,4,4 Nitro compounds such as 8-thioxanthone, 3,4,5,7-tetranitro-9-fluorenone, 3,5-dimethyl-3 ′,
5′-di-tert-butyl diphenoquinone, 3,
Diphenoquinone compounds such as 3 ', 5,5'-di-tert-butyldiphenoquinone;

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-oxadiazole, 2,5-di (4-N,
Oxadiazole compounds such as (N-diethylaminophenyl) -1,3,4-oxadiazole, styryl compounds such as 9- (4-diethylaminostyryl) anthracene, carbazole compounds such as N-ethylcarbazole, 1-phenyl -3- (4-Dimethylaminophenyl) pyrazolin, 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
Oxazole compounds such as-(2-chlorophenyl) oxazole, isoxazole compounds, thiazole compounds such as 2- (4-diethylaminostyryl) -6-diethylaminobenzothiazole, triphenylamine, 4,4′-bis [N -(3-methylphenyl) -N
-Phenylamino] biphenyl and the like, nitrogen-containing cyclic compounds such as stilbene compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, indole compounds, triazole compounds, etc., and condensation polycondensates such as anthracene, pyrene and phenanthrene. Ring compounds and the like.

Solvents for coating and laminating the photoreceptor include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and dichloroethane, tetrahydrofuran and dioxane. Ether solvents, ketones such as cyclohexanone, methyl ethyl ketone and acetone, esters such as ethyl acetate, ethyl cellosolve and ethyl cellosolve, and alcohols such as methanol, ethanol, isopolanol and butanol can be used.

As a coating apparatus, a roll coater, a spray coater, a dipping coater, a doctor blade or the like can be used. In recent years, a method has been proposed in which a charge transfer layer and a photosensitive layer of an organic electrophotographic photosensitive member are formed by an evaporation method using an evaporation apparatus. For example, JP-A-2-25
As described in 1849 and the like, the monomers and oligomers of the present invention can be applied to these methods. Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 A polyamide resin (Toray, CM-80) was placed on an aluminum plate.
After an undercoat layer having a dry thickness of 0.6 μm was formed, the coating solution containing the following trisazo pigment was blade-coated to form a charge generation layer having a dry thickness of 0.4 μm. Next, the oligomer of Synthesis Example 4 and 1,1-bis (phenylcarbonyldioxy-1,4-phenylene) cyclohexane were dissolved in methylene chloride at a weight ratio of 5: 1 to coat a charge transfer layer having a solid content of 18 wt%. A liquid was prepared. This coating solution was applied by blade coating and dried at 120 ° C. for 30 minutes. Next, it was cured at a drying temperature of 210 ° C. for 1 hour, and a charge transfer layer having a dry film thickness of 12 μ was laminated.

[0064]

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Example 2 The oligomer of Synthesis Example 5 in Example 1 was replaced with a solid content of 20 w
A charge transfer layer having a dry film thickness of 11 μm was formed in the same manner as in Example 1 except that a t% methylene chloride solution was prepared and coated by blade coating.

Example 3 In Example 1, the oligomer of Synthesis Example 6 and 1,1,1-
A dry film was prepared in the same manner as in Example 1 except that a methylene chloride solution having a solid content of 12 wt% was prepared by mixing tris (4-hydroxyphenyl) ethane in a weight ratio of 3: 2, and was coated by blade coating. A 10 μm thick charge transfer layer was formed.

Comparative Example 1 An undercoat layer and a charge generation layer were formed on an aluminum plate in the same manner as in Example 1. Then, according to the synthesis method disclosed in Example 3 of JP-A-64-9964, the weight average molecular weight was 30.
A 0000 polyarylamine compound was obtained, and a 20 μm charge transfer layer was provided on the charge generation layer according to the method disclosed in Example 4.

Comparative Example 2 An undercoat layer and a charge generation layer were formed on an aluminum plate in the same manner as in Example 1. Next, a photoconductor was prepared in the same manner as in Example 1, except that a charge transport layer having a dry film thickness of 15 μm was formed using a coating solution obtained by dissolving 5 g of triphenylamine and 5 g of polycarbonate in 40 g of methylene chloride.

The obtained photoreceptor was negatively charged by an electrophotographic characteristic evaluation device EPA8100 manufactured by Kawaguchi Electric Co., Ltd., and the receiving potential (Vm), the residual potential (Vr), and the white sensitivity (E _1/2 ) using a halogen lamp were 5 lux. The exposure intensity was measured. In addition, a wiping test was performed using gauze soaked with toluene. The Empitz hardness was evaluated at an angle of 45 degrees. Table 1 shows the results.

[0070]

[Table 1]

Wipe test: OK (not easily wiped): NG ( easily wiped) Empitz hardness: 100 g weight

[0072]

The use of the electrophotographic photoreceptor containing the polymer having a triphenylamine structural unit according to the present invention and having a molecular structure in which the polymer is three-dimensionalized by a carbonate bond is used to increase the mechanical strength. It is possible to provide an organic electrophotographic photoreceptor having a high solvent resistance and an excellent property.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 5/00

Claims (2)

(57) [Claims] 1. An electrophotographic photosensitive member having an organic photosensitive layer provided on a support, wherein a part or the whole of the photosensitive layer is a polymer having an arylamine structural unit, and the polymer is three-dimensionally formed by a carbonate bond. An electrophotographic photoreceptor comprising a polymer having an improved molecular structure. 2. A photosensitive layer containing an arylamine oligomer having a hydroxyl group and / or a phenyl carbonate group or an alkyl carbonate group having 1 to 4 carbon atoms at the terminal and containing a carbonate bond having a molecular weight of 1 × 10 ⁴ or less is heated. The method for producing an electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is cured.