JPH0784386A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To provide an electrophotographic receptor excellent in a photosensitive characteristic with large strength to heat and mechanical impact and manufactured at low cost. CONSTITUTION:An electrophotographic receptor contains at least one kind of diamine compound having a carbonate group expressed by a formula. In the formula, R<1>, R<2> represent a hydrogen atom, an alkyl group, or an aryl group, Y represents an allylene group or the like, X represents an alkylene group, a dialkylene ether group, or the like, (m) represents 0 or 1, and (n) represents an integer of 0-6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a photosensitive layer containing a specific compound.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as photoconductive materials for photoconductors used in electrophotography.
The term "electrophotographic method" generally means that a photoconductive photoconductor is first charged in a dark place by, for example, corona discharge, and then imagewise exposed to selectively dissipate the charge only in the exposed portion. An electrostatic latent image is obtained, and this latent image portion is developed with electroscopic fine particles (toner) composed of a coloring material such as a dye or pigment and a binder such as a polymer substance to be visualized to form an image. This is one of the image forming methods.

The basic characteristics required for a photoconductor in such an electrophotographic method are: (1) being able to be charged to an appropriate potential in a dark place, (2) being small in dissipation of a charge in a dark place, (3) It is possible to rapidly dissipate the charge by light irradiation.

By the way, in reality, each of the above-mentioned inorganic substances has various advantages and, at the same time, has various drawbacks. For example, selenium, which is widely used at present, sufficiently satisfies the above conditions (1) to (3), but the manufacturing conditions are difficult, the manufacturing cost is high, the selenium is not flexible, and it is processed into a belt shape. It is difficult and difficult to handle because it is sensitive to heat and mechanical shock. Cadmium sulfide and zinc oxide are used as photoconductors by dispersing them in a resin as a binder, but since they have mechanical defects such as smoothness, hardness, tensile strength and abrasion resistance, they can be repeated as they are. Can not be used.

In recent years, in order to eliminate the disadvantages of these inorganic substances, electrophotographic photoreceptors using photoconductive materials made of various organic substances have been proposed and some have been put to practical use. For example, poly-N-vinylcarbazole and 2,
A photoreceptor comprising 4,7-trinitrofluoren-9-one (described in U.S. Pat. No. 3,484,237), a photoreceptor obtained by sensitizing poly-N-vinylcarbazole with a pyrylium salt dye (Japanese Patent Publication No. 48-25658), a photoreceptor containing an organic pigment as a main component (JP-A-47-3
No. 7543), a photoreceptor containing a eutectic complex of a dye and a resin as a main component (described in JP-A-47-10735), and a photoreceptor obtained by dye-sensitizing a triphenylamine compound ( U.S. Pat. No. 3,180,730), a photoconductor using an amine derivative as a charge transport material (Japanese Patent Laid-Open No. Sho 5)
7-195254), a photoconductor using poly-N-vinylcarbazole and an amine derivative as a charge transport material (JP-A-58-1155), and a benzidine compound among polyfunctional tertiary amine compounds as a photoconductive material. Photoreceptor used (U.S. Pat. No. 3,265,496, Japanese Patent Publication No. 3)
No. 9-11546 and Japanese Patent Laid-Open No. 53-27033). These photoconductors have excellent properties and are considered to be of high value practically.However, in consideration of various demands on the photoconductor in the electrophotographic method, these demands are still insufficient. It is the actual situation that nothing satisfying the above is obtained.

On the other hand, a photoreceptor using a compound having a carbonate group as a photoconductive material is disclosed in US Pat.
No. 517, No. 4,806,443, No. 4,806,4
44, JP-A-3-221522, and JP-A-4-11.
No. 627. However, since the compound having a carbonate group used in these photoconductors is a polymer compound, a purification method such as column chromatography or recrystallization for obtaining a sufficient purity required for the photoconductive material used in the photoconductors. However, it has a drawback that distillation, sublimation purification, etc. cannot be performed easily. Therefore, the photoconductor using these polymer photoconductive materials cannot fully remove the impurities contained therein, and thus may not satisfy the above-mentioned requirements.

Further, as a photoreceptor, a photoreceptor in which a low molecular weight photoconductive material is dissolved and dispersed in a binder resin solution and cast to form a photosensitive layer is widely used. However, when the photosensitive layer is formed by mixing the above-mentioned polymer photoconductive material and another binder resin, depending on the binder resin, the resin mixed solution is liable to be whitened (gelled) or separated into layers to obtain a uniform photosensitive layer. However, there is a problem that the electrostatic characteristics are adversely affected and the durability is deteriorated.

Further, in JP-A-3-221522, whitening (gelation) of a coating liquid, partial crystallization of the photosensitive layer, and cracks (cracks) when a photosensitive layer is formed by using a polymer photoconductive material alone ), It is necessary to adjust the copolymerization ratio and the viscosity in order to solve the problem.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the various drawbacks of the conventional photoconductive materials described above.
An object of the present invention is to provide an electrophotographic photosensitive member that can sufficiently satisfy the conditions required in the electrophotographic method. Another object of the present invention is to provide an electrophotographic photosensitive member which is easy to manufacture, relatively inexpensive, and excellent in durability.

[0010]

According to the present invention, at least one diamine compound having a carbonate group represented by the following general formula (I) (formula 1) is contained as an active ingredient on a conductive support. Provided is an electrophotographic photoreceptor having a photosensitive layer.

[Chemical 1] [Wherein R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
R ¹ and R ² may combine with N to form a ring. Y is a substituted or unsubstituted arylene group or the following formula

[Chemical 2] (In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted arylene group, R ³ and R ⁴ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and 1 is 1 Alternatively, R ¹ and Y may together form a ring.
X is a substituted or unsubstituted alkylene group, a dialkylene ether group, a substituted or unsubstituted arylene group, or the following formula —Ar ³ —Z—Ar ⁴ — (wherein Ar ³ , Ar ⁴ are substituted or unsubstituted) Represents an arylene group, Z is a substituted or unsubstituted alkylene group, a dialkylene ether group, a substituted or unsubstituted cycloalkylidene group, an oxygen atom,
Represents a sulfur atom and vinylene group. ) Is represented. m is 0
Alternatively, 1 and n represent an integer of 0 to 6. ]

The compound is represented by the following general formula (II)
(Chemical formula 3)

[Chemical 3] And a hydroxy compound represented by the general formula (III)

[Chemical 4] It is produced by reacting with a bis (chloroformate) compound represented by

The diamine compound having a carbonate group represented by the general formula (I) will be described in more detail. In the diamine compound having a carbonate group represented by the general formula (I), the following may be mentioned as specific examples of R ^{1 to} R ⁴ , Ar ^{1 to} Ar ⁴ , X, Y and Z or as substituents thereof. You can (1) Hydrogen atom (-H) (2) Halogen atom (-X) Fluorine, chlorine, bromine and iodine are mentioned. (3) a cyano group (-CN) (4) a nitro group (-NO ₂₎ (5) hydroxy group (-OH) (6) alkyl group _{^{(-R 5), C 1 ~C}} 12 especially C ₁ ~
C ₉ and more preferably C _{1 to} C ₄ linear or branched alkyl groups, and these alkyl groups further include fluorine atom, hydroxyl group, cyano group, C _{1 to} C ₄ alkoxy group, phenyl group or halogen. A phenyl group substituted with an atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group may be contained. Specifically, a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, s-
Butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-phenylethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2
-Methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group,
4-phenylbenzyl group etc. are mentioned. (7) Alkoxy group (—OR ⁵ ): R ⁵ represents the alkyl group defined in (6). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano. Examples thereof include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group and a trifluoromethoxy group. (8) an alkylthio group (-SR ^5): R ⁵ represents an alkyl group specified in (6). Specifically, a methylthio group,
Examples thereof include an ethylthio group, a benzylthio group and a hydroxyethylthio group. (9) an alkylene group ^{(-R 6 -): - R} 6 - represents a divalent group derived from an alkyl group specified in (6). Specifically, methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene group. , Phenylmethylene group, 4-methylphenylmethylene group, 2,2-
Examples thereof include a propylene group, a 2,2-butylene group and a diphenylmethylene group. (10) dialkylene ether group (-R ⁷ -O-R
⁸ −): R ⁷ and R ⁸ represent the alkylene group defined in (9). Specific examples thereof include a dimethylene ether group, a diethylene ether group and a methylene ethylene ether group. (11) Cycloalkylidene group (group represented by the following chemical formula 5):

[Chemical 5] Specific examples thereof include a 1,1-cyclopentylidene group, a 1,1-cyclohexylidene group and a 1,1-cyclooctylidene group. (12) Aryl group (—Ar ⁵ ): represents a carbocyclic aromatic group or a heterocyclic aromatic group, and is specifically a phenyl group, biphenyl group, terphenyl group, pentalenyl group, indenyl group, naphthyl group. , An azulenyl group, a heptanenyl group, a biphenylenyl group, an as-indacenyl group,
Fluorenyl group, s-indacenyl group, acenaphthylenyl group, preadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenyl group, triphenyllenyl group, Pyrenyl group, chrysenyl group, and naphthacenyl group, pyridyl group, pyrimidyl group, pyrazinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, coumarinyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, Dibenzofuranyl group, benzothienyl group, dibenzothionyl group, indolyl group, carbazolyl group, pyrazolyl group, imidazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, indazolyl group, benzothiazolyl group, pyridazyl group Group, cinnolinyl group, quinazolinyl group, quinoxalyl group, phthalazinyl group, phthalazine dionyl group, chromonyl group, naphthactonyl group, quinononyl group, o-sulfobenzoic acid imidyl group, maleic acid imidyl group, naphthalidinyl group, benzimidazolonyl group. Group, benzoxazolonyl group, benzothiazolonyl group,
Benzothiazothionyl group, quinazolonyl group, quinoxalonyl group, phthalazonyl group, dioxopyrimidinyl group, pyridonyl group, isoquinononyl group, isoquinolyl group, isothiazolyl group, benzisoxazolyl group, benzisothiazolyl group, indazolonyl group, acridinyl group , An acridonyl group, a quinazoline dionyl group, a quinoxaline dionyl group, a benzoxazine dionyl group, a benzoxazinyl group, and a naphthalimidyl group. Further, these aryl groups may have the substituents shown in (2) to (8). (13) aryloxy (-OAr ^5): Ar ⁵ is (1
It represents an aryl group defined in 2). Specific examples thereof include a phenoxy group, a 4-methylphenoxy group and a naphthoxy group. (14) an arylthio group (-SAr ^5): Ar ⁵ is (1
It represents an aryl group defined in 2). Specific examples include a phenylthio group and a naphthyltyl group. (15) Arylene group (—Ar ⁶ —): —Ar ⁶ — is (1
It represents a divalent group derived from the aryl group defined in 2). Specific examples thereof include a phenylene group, a biphenylylene group, a pyrenylene group and an N-ethylcarbazolylene group. (16) an amino group ^{(-N (R 9) (R} 10)): R 9, R 10
Are each independently a hydrogen atom, an alkyl group defined in (6),
It represents an aryl group defined in (12) and may jointly form a ring. Specifically, amino group, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino Group, a julolidyl group and the like. (17) Vinyl group (group represented by the following chemical formula 6 or chemical formula 7)

[Chemical 6]

[Chemical 7] (In the formula, R ¹¹ and R ¹² are (1) to (5), (12) to (1
In 4), R ¹³ and R ¹⁴ represent the substituents defined in (9), (10) and (15), j is an integer of 0 or 1 and W
Represents an oxygen atom, a sulfur atom, a vinylene group or an alkylene group. ) Specifically, a styryl group, 4-methylstyryl group, β-methylstyryl group, 4-chlorostyryl group, β-phenylstyryl group, β- (4-methylphenyl) styryl group, 4-phenyl-1, A 3-butaenyl group etc. can be mentioned.

Representative examples of hydroxy compounds and bis (chloroformate) compounds, which are the starting materials for the diamine compounds having a carbonate group used in the present invention, are shown in Tables 1, 2 and 3.

[0014]

[Table 1- (1)]

[0015]

[Table 1- (2)]

[0016]

[Table 1- (3)]

[0017]

[Table 1- (4)]

[0018]

[Table 1- (5)]

[0019]

[Table 2- (1)]

[0020]

[Table 3- (1)]

[0021]

[Table 3- (2)]

[0022]

[Table 3- (3)]

[0023]

[Table 3- (4)]

A photoreceptor using the photoconductive material of the present invention is
A photosensitive layer containing a photoconductive material containing one or more of the above-mentioned carbonate group-containing diamine compounds.
(2 ′, 2 ″, 2 ′ ″, or 2 ″ ″), but depending on how the photoconductive material containing the diamine compound having a carbonate group is applied, It can be used as shown in FIG. 2, FIG. 3, FIG. 4 or FIG.

The photosensitive member shown in FIG. 1 comprises a conductive support 1 on which a photosensitive layer 2 comprising a diamine compound having a carbonate group, a sensitizing dye and a binder (binder resin) is provided. The diamine compound here acts as a photoconductive substance, and the generation and transfer of charge carriers required for light attenuation are performed via the diamine compound. However, since the diamine compound has almost no absorption in the visible region of light, it is necessary to add a sensitizing dye having absorption in the visible region for sensitization for the purpose of forming an image with visible light. is there.

In the photosensitive member shown in FIG. 2, a photosensitive layer 2'wherein a charge generating substance 3 is dispersed on a conductive carrier 1 in a charge carrier medium 4 composed of a diamine compound having a carbonate group and a binder is provided. It has been done. The diamine compound here forms together with the binder (or the binder and the plasticizer) a charge carrier medium, while the charge generating substance 3 (charge generating substance such as an inorganic or organic pigment) generates a charge carrier. . In this case, the charge carrier medium 4 is mainly responsible for receiving the charge carriers generated by the charge generating substance 3 and carrying them. In this photoreceptor, the basic condition is that the charge generating substance and the diamine compound having a carbonate group do not overlap each other mainly in the visible wavelength region. This is because it is necessary to transmit light to the surface of the charge generating substance 3 in order to efficiently generate charge carriers in the charge generating substance 3.

The photosensitive member in FIG. 3 is a photosensitive member comprising a conductive support 1 and a charge generating layer 5 containing a charge generating substance 3 as a main component and a charge carrying layer 4 containing a diamine compound having a carbonate group. Layer 2 '' is provided. In this photoreceptor, the light transmitted through the charge transport layer 4 reaches the charge generation layer 5 and the charge carriers are generated in that region, while the charge transport layer 4 receives the injection of the charge carriers and carries them. The charge carriers necessary for light attenuation are generated by the charge generating substance 3, and the charge carriers are transported by the charge transport layer 4 (mainly the diamine compound works). Such a mechanism is the same as that explained for the photoconductor shown in FIG.

The photoconductor in FIG. 4 has a third charge generation layer 5
The charge transport layer 4 containing a diamine compound having a carbonate group is reverse to the stacking order, and the mechanism of generation and transport of the charge carriers can be the same as described above.
In this case, considering the mechanical strength, the protective layer 6 may be provided on the charge generation layer 5 as shown in FIG.

In order to actually prepare a photoconductor using the photoconductive material of the present invention, in the case of the photoconductor shown in FIG. 1, one kind of a diamine compound having a carbonate group in a solution in which a binder is dissolved. Alternatively, two or more kinds may be dissolved and a sensitizing dye may be further added thereto to prepare a liquid, which is coated on the conductive support 1 and dried to form the photosensitive layer 2.

The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 20 μm. The amount of the hydrazone compound in the photosensitive layer 2 is 30 to 70% by weight, preferably about 50% by weight, and the amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably 0.1. It is 5 to 3% by weight. As sensitizing dyes, triarylmethane dyes such as Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6B, Rhodamine B, Rhodamine 6G, Rhodamine G Extra, Eosin S, Erythrosine, Rose Bengal, Fluorescein are available. Such as xanthene dye, thiazine dye such as methylene blue, cyanine dye such as cyanine, 2,6-diphenyl-4- (N, N-dimethylaminophenyl) thiapyrylium perchlorate, benzopyrylium salt (Japanese Patent Publication No. No. 25658 gazette) and the like. In addition, these sensitizing charges may be used alone or in combination of two or more kinds.

Further, in order to produce the photoreceptor shown in FIG. 2, fine particles of the charge generating substance 3 are dispersed in a solution in which a diamine compound having one or more carbonate groups and a binder are dissolved. This may be applied on the conductive support 1 and dried to form the photosensitive layer 2 '.

The thickness of the photosensitive layer 2'is 3 to 50 μm, preferably 5 to 20 μm. The amount of the diamine compound having a carbonate group in the photosensitive layer 2'is 10 to 95.
%, Preferably 30 to 90% by weight, and the amount of the charge generating substance 3 in the photosensitive layer 2'is 0.1 to 50% by weight, preferably 1 to 20% by weight. Examples of the charge generating substance 3 include inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, cadmium sulfide-selenium, and α-silicon, and examples of organic pigments include CI Pigment Blue 25 (color index CI 21180).
CI Pigment Red 41 (CI 21200),
CI Acid Red 52 (CI 45100), CI Basic Red 3 (CI 45210), an azo pigment having a carbazole skeleton (JP-A-53-95033).
JP-A-53-1323), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), and azo pigments having a triphenylamine skeleton (JP-A-53-1323).
47), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (JP-A-54-1).
No. 2742), an azo pigment having a fluorenone skeleton (described in JP-A-54-22834), an azo pigment having a bisstilbene skeleton (JP-A-54-177).
No. 33), an azo pigment having a distyryloxadiazole skeleton (described in JP-A-54-2129), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-14967). Azo pigments such as CI Pigment Blue 16 (CI 74
100) and other phthalocyanine pigments, for example, CIVAT BROWN 5 (CI 73410), CIVAT Die (CI 73030) and other indigo pigments, Argos Scarlet B (manufactured by Bayer), Indanthren Scarlet R (manufactured by Bayer). And the like, such as perylene pigments. These charge-generating substances may be used alone or in combination of two or more.

Further, in order to prepare the photoreceptor shown in FIG. 3, a charge generating substance is vacuum-deposited on the conductive support 1 or more, or fine particles 3 of the charge generating substance are dissolved in a binder, if necessary. The charge generation layer 5 is prepared by applying a dispersion liquid dispersed in a different solvent and drying it, and further, if necessary, surface finishing and film thickness adjustment by a method such as buffing.
The charge transport layer 4 may be formed by applying a solution in which a diamine compound having one or more carbonate groups and a binder are dissolved thereon and drying. The charge generating material used for forming the charge generating layer 5 is the same as that described in the description of the photosensitive layer 2 '.

The charge generation layer 5 has a thickness of 5 μm or less, preferably 2 μm or less, and the charge transport layer 4 has a thickness of 3 to 50.
μm, preferably 5 to 20 μm is suitable. When the charge generation layer 5 is of a type in which the fine particles 3 of the charge generation layer substance are dispersed in a binder, the proportion of the fine particles 3 of the charge generation substance in the charge generation layer 5 is 10 to 95% by weight, preferably Is about 50 to 90% by weight. In addition, the charge transport layer 4
The amount of the compound in 10 to 95% by weight, preferably 3
It is 0 to 90% by weight.

To prepare the photoreceptor shown in FIG. 4, a solution in which a diamine compound having a carbonate group and a binder are dissolved is applied on the conductive support 1 and dried to form the charge transport layer 4. After that, a dispersion liquid in which fine particles of the charge generation layer substance are dispersed in a solvent in which a binder is dissolved, if necessary, is applied and dried on the charge transport layer by a method such as spray coating to form the charge generation layer 5. do it. The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG.
The photoconductor shown in FIG. 5 can be prepared by forming a protective layer 6 on the charge generation layer 5 of the photoconductor thus obtained by further spraying an appropriate resin solution by a method such as spray coating. As the resin used here, the binder described below can be used.

In the production of any of these photoreceptors, a metal plate or metal foil such as aluminum, a plastic film deposited with a metal such as aluminum, or a paper subjected to a conductive treatment is used as the conductive support 1. To be Further, as the binder, condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide are used. All insulating and adhesive resins can be used. If necessary, a plasticizer is added to the binder, and examples of such a plasticizer include halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate and the like.

Further, the photoreceptor obtained as described above may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include polyamide, nitrocellulose,
Aluminum oxide or the like is preferable, and the film thickness is preferably 1 μm or less. To make a copy using the photoreceptor of the present invention,
After the photosensitive surface is charged and exposed, it is developed and, if necessary, transferred to paper or the like. The photoconductor of the present invention has excellent advantages such as high sensitivity and high flexibility.

[0038]

EXAMPLES The present invention will be described below with reference to examples. Compound NO. Of diamine compound having carbonate group Is the hydroxy compound No. which is the raw material. And bis (chloroformate) compound NO. Expressed as a combination of. In addition,
In the following examples, all parts are parts by weight. [Synthesis Example] 4-hydroxytriphenylamine (hydroxy compound No. 1) 3.14 g (12.0 mmo)
l) and 1.86 g (14.4 mmol) of quinoline were dissolved in 20 ml of dry dichloromethane, and 4,4'-isopropylidenediphenol bis (chloroformate) [bis (chloroformate) compound NO.
11] A solution prepared by dissolving 2.12 g (6.00 mmol) in 20 ml of dry dichloromethane was added dropwise at room temperature over 15 minutes, and further stirred at 40 ° C. for 4 hours. The contents were washed with a separating funnel three times with water and once with a saturated saline solution, dried over magnesium sulfate and then concentrated under reduced pressure to obtain a green oily substance. This is treated with a silica gel column [eluent: toluene / n-hexane = (3/1) Vo
l. ] And is recrystallized in a C-hexane-toluene mixed solvent to give a colorless plate-like diamine compound having a polycarbonate group represented by the following structural formula (Formula 8) [Compound No. 1-11] was obtained (2.52 g, yield 52.3%). The melting point was 204.0 to 205.5 ° C.

[Chemical 8] The elemental analysis values were as follows as C ₅₃ H ₄₂ N ₂ O ₆ .

Example 1 As a charge-generating substance, 76 parts of Diane Blue (CI Pigment Blue 25, CI21180), 1260 parts of a 2% tetrahydrofuran solution of a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) and 3700 parts of tetrahydrofuran were placed in a ball mill. The obtained dispersion liquid was pulverized and mixed with a doctor blade to form a charge generating layer having a thickness of about 1 μm on the aluminum surface of a conductive aluminum-deposited polyester base, which was then dried. . On the other hand, the compound N is used as the charge carrier.
o. 2-11 parts of a diamine compound having a carbonate group of 3-11, a polycarbonate resin (Panlite K1300,
2 parts of Teijin Co., Ltd. and 16 parts of tetrahydrofuran were mixed and dissolved to form a solution, which was then applied onto the charge generation layer using a doctor blade, and then at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes. After being dried, a charge carrying layer having a thickness of about 20 μm was formed, and the photoconductor No. Created 1.

Examples 2 to 21 Photoreceptor No. 1 was carried out in the same manner as in Example 1 except that the charge generating substance and the charge carrier substance (diamine compound having a carbonate group) were replaced with those shown in Table 4. 2-21 were created.

[0041]

[Table 4- (1)]

[0042]

[Table 4- (2)]

[0043]

[Table 4- (3)]

[0044]

[Table 4- (4)]

Example 22 Selenium was vacuum-deposited to a thickness of about 1 μm on an aluminum plate having a thickness of about 300 μm to form a charge generation layer. Then No. 3-11 of a diamine compound having a carbonate group of 3-11, 3 parts of a polyester resin (Polyester Adhesive 49000 manufactured by DuPont) and 45 parts of tetrahydrofuran are mixed and dissolved to prepare a charge-transporting layer-forming liquid, It was applied onto the generating layer (selenium vapor deposition layer) using a doctor blade, naturally dried, and then dried under reduced pressure to form a charge transport layer having a thickness of about 10 μm. I got 22.

Example 23 A perylene pigment represented by the following structural formula (Formula 8) instead of selenium.

[Chemical 8] To form a charge generation layer (thickness is about 0.6 μm), and No. Photoconductor No. 3 was carried out in the same manner as in Example 22 except that the diamine compound having a carbonate group of 3-11 was used. 23 was created.

Example 24 A mixture of 1 part of Diane Blue (same as that used in Example 1) and 158 parts of tetrahydrofuran was pulverized and mixed in a ball mill, and then No. 12 parts of a diamine compound having a carbonate group of 3-11, polyester resin (Polyester Adhesive 490 manufactured by DuPont)
00) 18 parts and further mixed to obtain a photosensitive layer forming liquid, which is applied onto an aluminum vapor-deposited polyester film using a doctor blade and dried at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of about 16 μm. Forming the photosensitive member No. 24 was created.

Example 25 On a polyester film substrate vapor-deposited on aluminum,
The charge transport layer coating liquid used in Example 1 was blade coated in the same manner as in Example 1, and then dried to form a charge transport layer having a thickness of about 20 μm. Bisazo pigment (P-2) 13.
5 parts, polyvinyl butyral (trade name: XYHL Union Carbide Plastic Co., Ltd.) 5.4 parts, THF 6
After 80 parts and 1020 parts of ethyl cellosolve were pulverized and mixed in a ball mill, 1700 parts of ethyl cellosolve were added and mixed by stirring to obtain a charge generation layer coating liquid. This coating solution is spray-coated on the above charge transport layer, and the coating is carried out at 100 ° C. for 1 hour.
It was dried for 0 minutes to form a charge generation layer having a thickness of about 0.2 μm. Further, a methanol / n-butanol solution of a polyamide resin (trade name: CM-8000, manufactured by Toray) is spray-coated on the charge generation layer and dried at 120 ° C. for 30 minutes to form a protective layer having a thickness of about 0.5 μm. To form photoconductor N
o. 25 was created.

The photoconductor No. 1-25
For the above, using a commercially available electrostatic copying paper tester (type SP428 manufactured by KK Kawaguchi Denki Seisakusho), a corona discharge of -6KV or + 6KV was performed for 20 seconds to charge the sample, and then the sheet was left in a dark place for 20 seconds, and the surface at that time was measured. The potential Vpo (volt) is measured, and then the tungsten lamp light is irradiated so that the illuminance on the surface of the photoconductor becomes 4.5 lux, and the time (second) until the surface potential becomes 1/2 of Vpo is obtained. , Exposure amount E
½ (lux · sec) was calculated. The results are shown in Table 5.

[0050]

[Table 5]

Further, each of the above photoconductors was charged by using a commercially available electrophotographic copying machine, and then light was irradiated through the original drawing to form an electrostatic latent image, which was developed with a dry developer. When the obtained image (toner image) was electrostatically transferred onto plain paper and fixed, a clear transferred image was obtained. Even when a wet type developer was used as the developer, a clear transfer image was similarly obtained.

[0052]

The photoconductor using the photoconductive material of the present invention is not only excellent in photosensitivity but also has high strength against heat and mechanical shock and can be manufactured at low cost. .

[Brief description of drawings]

FIG. 1 is a sectional view of a specific example of an electrophotographic photosensitive member of the present invention enlarged in a thickness direction.

FIG. 2 is a sectional view of another specific example of the electrophotographic photosensitive member of the present invention enlarged in the thickness direction.

FIG. 3 is a sectional view of another specific example of the electrophotographic photosensitive member of the present invention enlarged in the thickness direction.

FIG. 4 is a sectional view of another specific example of the electrophotographic photosensitive member of the present invention enlarged in the thickness direction.

FIG. 5 is a sectional view of yet another specific example of the electrophotographic photosensitive member of the present invention enlarged in the thickness direction.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Conductive support 2, 2 ', 2' ', 2' '', 2 '' '' ... Photosensitive layer 3 ... Charge generating substance 4 ... Charge carrier medium or charge carrier layer 5 ... Charge generating layer 6 ... Protection layer

Claims (1)

[Claims] 1. An electron having a photosensitive layer containing, on an electrically conductive support, at least one diamine compound having a carbonate group represented by the following general formula (I) (Formula 1) as an active ingredient. Photoreceptor for photography. [Chemical 1] [Wherein R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
R ¹ and R ² may combine with N to form a ring. Y is a substituted or unsubstituted arylene group or the following formula: (In the formula, Ar ¹ and Ar ² represent a substituted or unsubstituted arylene group, R ³ and R ⁴ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and l is 1 Alternatively, R ¹ and Y may together form a ring.
X is a substituted or unsubstituted alkylene group, a dialkylene ether group, a substituted or unsubstituted arylene group, or the following formula —Ar ³ —Z—Ar ⁴ — (wherein Ar ³ , Ar ⁴ are substituted or unsubstituted) Represents an arylene group, Z is a substituted or unsubstituted alkylene group, a dialkylene ether group, a substituted or unsubstituted cycloalkylidene group, an oxygen atom,
Represents a sulfur atom and vinylene group. ) Is represented. m is 0
Alternatively, 1 and n represent an integer of 0 to 6. ]