JPH09304956A - Photosensitive body for electrophotography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive body for electrophotography which contains resin having charge transportation ability and high mechanical strength in a photosensitive layer, is highly sensitive, and has excellent durability. SOLUTION: A photosensitive layer which contains aromatic polycarbonate resin composed of repetitive unit shown by the following equation as an effective component is provided on a conducting support body. In the formula, n denotes an integer of 5 to 5000, Ar<1> and Ar<4> represent bivalent group of aromatic hydrocarbon, Ar<2> and Ar<3> represent aromatic hydrocarbon group, or complex ring group, and X represents aliphatic bivalent group, ringlike aliphatic bivalent group, etc.

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 a highly sensitive and highly durable electrophotographic photoreceptor containing an aromatic polycarbonate resin having a charge transporting ability in a photosensitive layer.

[0002]

2. Description of the Related Art In recent years, organic photoconductors (OPC) have been used in copying machines,
It is often used in printers. As a typical configuration example of the organic photoreceptor, a charge generation layer (CG) is formed on a conductive substrate.
L) and a charge transport layer (CTL) are sequentially laminated. The charge transport layer is a low molecular charge transport material (CT
M) and a binder resin. However,
The inclusion of the low molecular weight charge transport material reduces the mechanical strength originally possessed by the binder resin, which causes abrasion, scratches, cracks, etc. of the photoconductor and impairs the durability of the photoconductor. There is.

As a photoconductive polymer material, vinyl polymers such as polyvinylanthracene, polyvinylpyrene and poly-N-vinylcarbazole have been studied as charge transfer complex type photoconductors for a long time, but they are satisfactory in terms of photosensitivity. It wasn't possible. On the other hand, in order to improve the above-mentioned drawbacks of the laminated type photoreceptor, studies have been conducted on a polymer material having a charge transporting ability. For example, an acrylic resin having a triphenylamine structure [M. Stolka et al.
Polym. Sci. , Vol 21, 969 (198
3)], a vinyl polymer having a hydrazone structure (Jap)
an HardCopy '89P. 67) and a polycarbonate resin having a triarylamine structure (US Pat. Nos. 4,801,517, 4,806,443, 4,806,444, 4,937,165, and 4,959, US Pat. Nos. 288, 5,030,532, 5,034,296, 5,080,989, JP-A-64-9964, JP-A-3-221522.
JP-A-2-304456, JP-A-4-11627
JP-A-4-175337, JP-A-4-18371
Japanese Patent Laid-Open No. 4-31404, Japanese Patent Laid-Open No. 1333065
However, they have not been put to practical use yet.

In addition, M. A. Abkowitz et al. Compared a low molecular weight dispersion type and a polymerized polycarbonate using a tetraarylbenzidine derivative as a model compound, and obtained a result that a polymer system has a drift mobility lower by one digit. Physical Review B
46 6705 (1992)]. Although the cause of this is not clear, it suggests that there are problems in electrical characteristics such as sensitivity and residual potential, although the mechanical strength is improved by polymerizing.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances of the prior art, and by using an aromatic polycarbonate resin having a charge transporting ability,
It is an object of the present invention to provide an electrophotographic photoreceptor having high sensitivity and high durability.

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a novel aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) and a following general formula (II The present invention was found to solve the above problems by providing a photosensitive layer containing a novel aromatic polycarbonate resin composed of the repeating units represented by the formulas (3) and (III) as an active ingredient, and arrived at the present invention.

That is, the present invention is the following (1) to (4). (1) An electrophotographic photoreceptor, comprising a conductive layer and a photosensitive layer containing an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) as an active ingredient.

[0008]

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[Wherein n is an integer of 5 to 5000, Ar ¹
And Ar ⁴ are divalent groups of the same or different aromatic hydrocarbons,
Ar ² and Ar ³ represent the same or different substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heterocyclic groups. X is an aliphatic divalent group, a cycloaliphatic divalent group, or

[0010]

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(Wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and 1 and m are each independently 0. an to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -,

[0012]

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Z represents a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, and R ³ and R ⁴ are independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. (2) The following general formulas (II) and (II
For electrophotography, which is provided with a photosensitive layer comprising an aromatic polycarbonate resin which is composed of the repeating unit represented by I) and has a composition ratio of repeating units of 0 <k / (k + j) ≦ 1. Photoconductor.

[0014]

[Chemical 12]

[Wherein k is an integer of 5 to 5000 and j is 0]
To an integer of 5,000, Ar ¹ and Ar ⁴ are divalent groups of the same or different aromatic hydrocarbons, Ar ² and Ar ³ are the same or different substituted or unsubstituted aromatic hydrocarbon groups, or substituted or unsubstituted heterocyclic groups. Represents a ring group. X is an aliphatic divalent group, a cycloaliphatic divalent group, or

[0016]

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(Wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and 1 and m are each independently 0. an to 4 integer, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O -, - S -, - SO -, - SO 2 -,

[0018]

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Z represents a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, and R ³ and R ⁴ are independently substituted or unsubstituted. Represents an alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. (3) The aromatic polycarbonate resin has the following general formula (IV)
The electrophotographic photoreceptor according to (1) above, which is an aromatic polycarbonate resin comprising a repeating unit represented by:

[0020]

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[Wherein n, Ar ² , Ar ³ and X have the same meanings as in the above (1)] (4) An aromatic polycarbonate resin is represented by the following general formula (V):
And (III), which is an aromatic polycarbonate resin having a repeating unit composition ratio of 0 <k / (k + j) ≦ 1. body.

[0022]

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[Wherein k, j, Ar ² , Ar ³ and X have the same meanings as in the above (2)] As described above, the electrophotographic photoreceptor of the present invention has a tertiary amine structure in the photosensitive layer. An aromatic polycarbonate resin comprising a repeating unit represented by the general formula (I), or a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III) having a tertiary amine structure. Which contains an aromatic polycarbonate resin consisting of, but since these aromatic polycarbonate resins have charge transporting ability and high mechanical strength, the present photoreceptor has high sensitivity and high durability. . Hereinafter, the present invention will be described in more detail.

As described above, the electrophotographic photoreceptor of the present invention comprises an aromatic polycarbonate resin comprising the repeating unit represented by the general formula (I) or the repeating unit represented by the general formula (II) in the photosensitive layer. The aromatic polycarbonate resin contains a repeating unit represented by the general formula (III), and these aromatic polycarbonate resins are novel substances and are produced by the following method.

The aromatic polycarbonate resin of the present invention is
It can be produced by a method similar to the known method for producing a polycarbonate resin, which is a known method for producing a polycarbonate resin. That is, the aromatic polycarbonate resin comprising the repeating unit represented by the general formula (II) or the general formula (V) of the present invention has the following general formula (VI) or general formula (VI).
A transesterification method of a diol compound having a tertiary amino group represented by I) with a bisaryl carbonate,
It is produced by a phosgene method by solution or interfacial polymerization with phosgene, a bischloroformate method using a bischloroformate derived from a diol, or the like. At this time, by using a diol compound represented by the following general formula (VIII) together, an aromatic polycarbonate resin comprising a repeating unit represented by the above general formula (I) or (IV), and further by the above general formula ( An aromatic polycarbonate resin comprising a repeating unit represented by II) and a repeating unit represented by the general formula (III), a repeating unit represented by the general formula (V) and the general formula (II
An aromatic polycarbonate resin composed of the repeating unit represented by I) can be produced, whereby an aromatic polycarbonate resin having desired characteristics can be obtained. The ratio of the repeating unit represented by the general formula (II) to the repeating unit represented by the general formula (III), the repeating unit having a tertiary amino group represented by the general formula (V), and the general formula ( The ratio with the repeating unit represented by III) can be selected from a wide range depending on the desired characteristics.

[0026]

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HO-X-OH (VIII) [Ar ^{1 to} Ar ⁴ , X in the formulas are the same as defined above. Specific examples of the diol compound having a tertiary amino group represented by the general formula (VI) and the general formula (VII) are shown below. A
Specific examples of the case where r ² and Ar ³ are the same or different substituted or unsubstituted aromatic hydrocarbon groups and the case where they are substituted or unsubstituted heterocyclic groups include the following.

(1) Aromatic hydrocarbon group; phenyl group, naphthyl group as condensed polycyclic group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group , A chrysenyl group, a fluorenylidenephenyl group, a 5H-dibenzo [a, d] cycloheptenylidenephenyl group, a biphenylyl group as a non-condensed polycyclic group, a terphenylyl group, or

[0029]

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Here, W is -O-, -S-, -SO-,
-SO ₂ -, - CO- and represent divalent groups below.

[0031]

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It is represented by R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic hydrocarbon group. (2) Heterocyclic group: Thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like. The divalent group of the aromatic hydrocarbon represented by Ar ¹ and Ar ⁴ includes the divalent group of the aromatic hydrocarbon group represented by Ar ² and Ar ³ .

The above-mentioned aromatic hydrocarbon group and heterocyclic group may have the following groups as a substituent. Further, these substituents are represented as specific examples of R ^{5 in} the above general formula. (3) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(4) Alkyl group; preferably C _{1 to} C ₁₂
Particularly, C _{1 to} C ₈ , more preferably C _{1 to} C ₄ linear or branched alkyl groups, and these alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group, a C _{1 to} C ₄ alkoxy group, It may contain a phenyl group or a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, a methyl group,
Ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl 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 and the like can be mentioned.

(5) Alkoxy group (-OR ⁷ ); R ⁷ represents the alkyl group defined in (4) above. 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
-A cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, a trifluoromethoxy group and the like.

(6) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. This is C ₁ ~
An alkoxy group having C _4, may contain an alkyl group or a halogen atom C ₁ -C ₄ as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group and a 6-methyl-2-naphthyloxy group. . (7) Substituted mercapto group or aryl mercapto group;
Specific examples include a methylthio group, an ethylthio group, a phenylthio group, a p-methylphenylthio group and the like.

(8)

[0038]

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In the formula, R ⁸ and R ⁹ each independently represent an alkyl group or an aryl group defined in (4), and examples of the aryl group include a phenyl group, a biphenylyl group and a naphthyl group, and these are C ₁ alkoxy group -C _4, alkyl group, or a halogen atom C ₁ -C ₄ may contain a substituent group. It may also form a ring in cooperation with the carbon atom on the aryl group. Specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group,
Examples thereof include a dibenzylamino group, a piperidino group, a morpholino group, and a julolidyl group. (9) Examples include an alkylenedioxy group such as a methylenedioxy group, a methylenedithio group, an alkylenedithio group, and the like.

Specific examples of the diol compound represented by the general formula (VIII) are shown below. 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol,
Aliphatic diols such as diethylene glycol, triethylene glycol, polyethylene glycol and polytetramethylene ether glycol, and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol and cyclohexane-1,4-dimethanol are mentioned. To be

As the diol compound having an aromatic ring, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1
-Bis (4-hydroxyphenyl) cyclopentane,
2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-)
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl sulfone,
4,4′-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxydiphenyl sulfide, 3,3'-
Dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 2,
2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), Diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate), 1,3-bis (4-
Examples thereof include hydroxyphenyl) -tetramethyldisiloxane and phenol-modified silicone oil.

Cross-sectional views of the photoconductor of the present invention are shown in FIGS. The photoreceptor of the present invention contains one or more aromatic polycarbonate resins as described above in the photosensitive layer 2 (2 ',
2 ″, 2 ″ ″, 2 ″ ″, 2 ′ ″ ″), but depending on the way of applying these, FIG. 1, FIG. 2, FIG.
It can be used as shown in FIG. 4, FIG. 5 or FIG.

The photosensitive member shown in FIG. 1 comprises a conductive support 1 and a photosensitive layer 2 comprising a sensitizing dye, an aromatic polycarbonate resin, and a binder (binder resin) in some cases. The aromatic polycarbonate resin here acts as a photoconductive substance, and the generation and transfer of charge carriers required for light attenuation are performed via the aromatic polycarbonate resin. However, since the aromatic polycarbonate resin has almost no absorption in the visible region of light, for the purpose of forming an image with visible light, a sensitizing dye having absorption in the visible region is added for sensitization. There is a need.

In the photosensitive member shown in FIG. 2, a photosensitive layer 2'wherein a charge generating substance 3 is dispersed in a charge transport medium 4 composed of an aromatic polycarbonate resin alone or in combination with a binder is provided on a conductive support 1. It has been done. The aromatic polycarbonate resin here alone or in combination with a binder forms a charge transport medium, while the charge generating substance 3
(Charge-generating substances such as inorganic or organic pigments) generate charge carriers. In this case, the charge transport medium 4 is mainly responsible for receiving the charge carriers generated by the charge generating substance 3 and transporting them. The basic condition of this photoreceptor is that the charge generating substance and the aromatic polycarbonate resin do not overlap each other in the absorption wavelength region mainly in the visible 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 aromatic polycarbonate resin represented by the repeating unit of the general formula (I) has almost no absorption in the visible region and is particularly effective when combined with the charge generating substance 3 which absorbs light in the visible region and generates a charge carrier. Its characteristic is that it works as a charge transport material. A low molecular weight charge transport material may be used in combination in the charge transport medium 4.

The photoconductor in FIG. 3 is a photoconductive layer 2'having a laminate of a charge generation layer 5 having a charge generation substance 3 as a main component and a charge transport layer 4 containing an aromatic polycarbonate resin on a conductive support 1. '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 transports them. ,
Generation of charge carriers necessary for light attenuation is performed by the charge generating substance 3, and transport of charge carriers is performed by the charge transport layer 4. Such a mechanism is the same as that explained for the photoconductor shown in FIG.

The charge transport layer 4 is formed by using the aromatic polycarbonate resin of the present invention alone or in combination with a binder. In addition, the aromatic polycarbonate resin of the present invention may be contained in the charge generation layer 5 in order to increase the charge generation efficiency. For the same purpose, a low molecular weight charge transport material may be used in combination in the photosensitive layer 2 ″. The same applies to the photosensitive layers 2 ″ ″ to 2 ″ ″ ″ described below.

The photoreceptor shown in FIG. 4 has a protective layer 6 provided on the charge transport layer 4. In the case of this constitution, a protective layer is formed on the charge transport layer 4 in combination with the aromatic polycarbonate resin or the binder of the present invention. As a matter of course, it is effective to form it on the low molecular weight dispersion type charge transport layer which has been often used conventionally. The photosensitive layer 2'shown in FIG.
A protective layer may likewise be provided on top. The photoreceptor in FIG. 5 is obtained by reversing the stacking order of the charge generation layer 5 and the charge transport layer 4 containing an aromatic polycarbonate resin in FIG. 3, and the mechanism of generation and transport of charge carriers is the same as that described above. You can do the same. 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 produce the photoreceptor of the present invention, the photoreceptor shown in FIG. 1 is dissolved by dissolving one or more aromatic polycarbonate resins in combination with a binder, and further increasing the amount. A photosensitive layer 2 may be formed by preparing a solution containing an infectious agent, coating the solution on the conductive support 1, and drying the solution.

The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 20 μm. The amount of the aromatic polycarbonate resin in the photosensitive layer 2 is 30 to 100% by weight,
The amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably 0.5 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,
Examples include xanthene dyes such as eosin S, erythrosine, rose bengal and fluorescein, thiazine dyes such as methylene blue, and cyanine dyes such as cyanine. 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 one or more aromatic polycarbonate resins or binders are dissolved together and the conductive particles are made conductive. The photosensitive layer 2 ′ may be formed by coating on the support 1 and drying.

The thickness of the photosensitive layer 2'is 3 to 50 μm, preferably 5 to 20 μm. The amount of the tertiary amine compound in the photosensitive layer 2'is 40 to 100% by weight,
Further, the amount of the charge generating substance 3 in the photosensitive layer 2'is 0.1 to
It is 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 CI2118).
0), CI Pigment Red 41 (CI2120
0), CI Acid Red 52 (CI4510
0), CI Basic Red 3 (CI4521)
0), an azo pigment having a carbazole skeleton (JP-A-53-53
-95033), an azo pigment having a distyrylbenzene skeleton (JP-A-53-133445), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132347), and dibenzothiophene. Azo pigments having a skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), azo pigments having a fluorenone skeleton (JP-A-54). No. 22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), and an azo pigment having a distyryloxadiazole skeleton (JP-A-54-21).
29), azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967).
Azo pigments such as CI Pigment Blue 16
Phthalocyanine-based pigments such as (CI74100), for example, CIVAT BROWN 5 (CI73410), indigo-based pigments such as CIVAT Die (CI73030), Argos Scarlet B (manufactured by Bayer), Indanthren Scarlet R (manufactured by Bayer), etc. Perylene pigments and the like. These charge-generating substances may be used alone or in combination of two or more.

Further, to manufacture the photoconductor shown in FIG. 3,
A charge generating substance is vacuum-deposited on the conductive support 1, or a dispersion liquid in which fine particles 3 of the charge generating substance are dispersed in a suitable solvent in which a binder is dissolved if necessary is applied and dried. If necessary, surface finishing, film thickness adjustment, etc. are performed by a method such as buffing to form the charge generation layer 5, and one or more aromatic polycarbonate resins or a binder is used together and dissolved on the charge generation layer 5. The solution may be applied and dried to form the charge transport layer 4. The charge generating substance used for forming the charge generating layer 5 is the same as that described for 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 100% by weight, preferably Is about 50 to 100% by weight. The amount of the compound in the charge transport layer 4 is 40 to 100% by weight. As described above, the photosensitive layer 2 ″ in FIG. 3 may contain a low-molecular weight charge transporting substance, and the charge transporting substance used here includes the following.

Oxazole derivatives and oxadiazole derivatives (JP-A-52-139065 and JP-A-52-1390)
No. 66), an imidazole derivative, a triphenylamine derivative (described in JP-A-3-285960), a benzidine derivative (described in JP-B-58-32372), and an α-phenylstilbene derivative (JP-A-5).
7-73075), hydrazone derivatives (JP-A-55-154955, JP-A-55-156954,
No. 55-52063, No. 56-81850, etc.), triphenylmethane derivative (Japanese Patent Publication No. 5-1
0983), anthracene derivatives (described in JP-A-51-94829), styryl derivatives (described in JP-A-56-29245 and JP-A-58-198043), and carbazole derivatives (JP-A-SHO). 58-585
52), pyrene derivatives (JP-A-2-948)
No. 12)) and the like.

To make the photoreceptor shown in FIG.
The protective layer 6 is provided by dissolving and coating the aromatic polycarbonate resin of the present invention, alone or in combination with a binder, on the photoreceptor shown in FIG. The thickness of the protective layer is 0.1
It is preferably 5 to 10 μm. The amount of the aromatic polycarbonate resin of the present invention in the protective layer 6 is 40 to 100% by weight.
It is.

In order to prepare the photosensitive member shown in FIG. 5, a solution in which an aromatic polycarbonate resin or a binder is used in combination and dissolved is coated on the conductive support 1 and dried to form the charge transport layer 4. The charge generation layer 5 may be formed by applying a dispersion liquid in which fine particles of the charge generation layer substance are dispersed in a solvent in which a binder is dissolved on the charge transport layer, if necessary, by coating and drying by a method such as spray coating. . The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG. By forming the above-mentioned protective layer 6 on the charge generation layer 5 of the thus obtained photoreceptor, the photoreceptor shown in FIG. 6 can be prepared. In the production of any of these photoconductors, a metal plate or metal foil such as aluminum, a plastic film on which a metal such as aluminum is vapor-deposited, or a paper subjected to a conductive treatment is used as the conductive support 1.

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. However,
All insulating and adhesive resins can be used. A plasticizer is optionally added to the binder, and examples of such a plasticizer include halogenated paraffin, dimethylnaphthalene, and dibutyl phthalate. Further, if necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer, and a lubricant can be added. Further, in the photoreceptor obtained as described above, an adhesive layer or a barrier layer can be provided between the conductive support and the photosensitive layer, if necessary. Materials used for these layers are polyamide, nitrocellulose, aluminum oxide, etc., and the film thickness is 1 μm.
m or less is preferable.

To make a copy using the photoreceptor of the present invention,
After the photosensitive surface is charged and exposed, it is developed and transferred to paper or the like if necessary. The photoreceptor of the present invention has high sensitivity,
It also has excellent durability.

[0057]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to examples. In the following examples, all parts are parts by weight. Production Example 1 As a starting material, a compound having a tertiary amino group having the following structure was used.

[0058]

[Chemical 21]

46 ml of dry THF was treated with 1,3-bis [N-
5.77 g (0.013 mol) of (3-hydroxyphenyl) -N-phenylamino] benzene and 3.95 g (0.039 mol) of triethylamine were dissolved. 3.33 g (0.0137 mol) of 1,6-hexanediol bischloroformate was added to this solution with dry THF14.
What was melt | dissolved in ml was dripped over 30 minutes under water cooling. After the addition is complete, the viscous mixture is stirred for a further 15 minutes,
0.28 g phenol dissolved in 5 ml dry THF was added. After stirring for 5 minutes, the resulting viscous mixture was precipitated in methanol and the crude product was filtered off. This product was subjected to THF dissolution-methanol precipitation treatment twice,
The precipitate was collected by filtration and dried to obtain a polycarbonate resin (compound No. 1) having the following structural formula. The obtained target product is 7.1.
The yield was 90.1% with 9 g, and the glass transition point was 69.
8 ° C.

[0060]

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When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Number average molecular weight 30400 Weight average molecular weight 73900 From the infrared absorption spectrum (film) of this product, 17
At 60 cm ⁻¹ , absorption based on C═O stretching vibration of carbonate was observed. The results of elemental analysis were as follows.

[0062] Production Examples 2 to 6 Similarly, aromatic polycarbonate resins (Compound Nos. 2 to 6) shown in Table 1 were obtained.

[0063]

[Table 1]

[0064]

[Table 2]

Examples are shown below, but the aromatic polycarbonate resin No. of the present invention in the examples corresponds to the above compound No. Example 1 A solution of a polyamide resin (CM-8000: manufactured by Toray Industries, Inc.) dissolved in a mixed solvent of methanol / butanol was applied on an aluminum plate with a doctor blade, and naturally dried to form an intermediate layer of 0.3 μm. A bisazo compound represented by the following formula as a charge generating substance is pulverized by a ball mill in a mixed solvent of cyclohexanone and methyl ethyl ketone.
The obtained dispersion was applied with a doctor blade and naturally dried to form a charge generation layer having a thickness of about 1 μm.

[0066]

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Next, the polycarbonate resin No. 1 obtained in Preparation Example 1 as a charge transport material was dissolved in dichloromethane, the solution was applied onto the charge generation layer with a doctor blade, air-dried, and then at 120 ° C. After being dried for 20 minutes, a charge transport layer having a thickness of about 20 μm was formed to form a photoconductor No. 1
Was produced.

Examples 2 to 6 The procedure of Example 1 was repeated except that the polycarbonate resin (Compound Nos. 2 to 6) used in Example 1 was replaced with the polycarbonate resin represented by Compound No. 1 described above. Photosensitive members No. 2 to 6 were prepared. Electrostatic copying paper tester commercially available for the photoconductors No. 1 to 6 produced in this way
[Kawaguchi Denki Seisakusho SP428 type] in the dark -6k
After the corona discharge of V was performed for 20 seconds to charge the photoreceptor, the surface potential V _m (V) of the photoconductor was measured, and the surface potential V ₀ (V) was measured after the photoreceptor was left in the dark for 20 seconds. Then, the illumination of the tungsten lamp light on the surface of the photoconductor is 4.5 lu.
Irradiation was performed so as to obtain x, the time (second) until V ₀ became 1/2 was obtained, and the exposure amount E _1/2 (lux · sec) was calculated. The results are shown in Table 2.

[0069]

[Table 3]

[0070]

EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention has an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (I) having a tertiary amine structure or a tertiary amine structure in the photosensitive layer. The aromatic polycarbonate resin containing the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III) has a charge transporting ability. And because it has high mechanical strength,
The photosensitive member has high sensitivity and high durability.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a layer structure of an electrophotographic photoreceptor according to the present invention,

FIG. 2 is a sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the present invention,

FIG. 3 is a sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the present invention,

FIG. 4 is a cross-sectional view showing another example of the layer constitution of the electrophotographic photoreceptor according to the present invention,

FIG. 5 is a cross-sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the present invention,

FIG. 6 is a cross-sectional view showing another example of the layer structure of the electrophotographic photoreceptor according to the present invention,

[Explanation of symbols]

 1 Conductive Support 2, 2 ', 2 ", 2'", 2 "", 2 '"" Photosensitive Layer 3 Charge Generating Material 4 Charge Transport Layer or Charge Transport Medium 5 Charge Generation Layer 6 Protective layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Inventor Chihaya Adachi 1-3-3 Nakamagome, Ota-ku, Tokyo In stock company Ricoh (72) Inventor Chiaki Tanaka 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh stock company (72) Inventor Akira Katayama 1-3-6 Nakamagome, Ota-ku Tokyo In-house company Ricoh (72) Inventor Mitsutoshi Anzai 66-2, Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Within Hodogaya Chemical Industry Co., Ltd. Within the corporation

Claims (4)

[Claims] 1. A photoreceptor for electrophotography, comprising a photosensitive layer provided on a conductive support, the photosensitive layer containing an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) as an active ingredient. Embedded image [In the formula, n is an integer of 5 to 5000, Ar ¹ and Ar ⁴ are divalent groups of the same or different aromatic hydrocarbons, Ar ² and Ar ³
Represents the same or different, substituted or unsubstituted aromatic hydrocarbon group, or substituted or unsubstituted heterocyclic group.
X is an aliphatic divalent group, a cycloaliphatic divalent group, or (Here, R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and 1 and m are each independently 0 to 4 Is an integer, Y is a single bond, 1 to 12 carbon atoms
A linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, ## STR3 ## Z represents a divalent group of an aliphatic hydrocarbon, and a
Is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ , R ⁴
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ] 2. An aromatic polycarbonate resin comprising repeating units represented by the following general formulas (II) and (III) on a conductive support, and the composition ratio of the repeating units is 0 <k / (k + j) ≦ 1. An electrophotographic photoreceptor, comprising a photosensitive layer containing as an active ingredient. Embedded image [In the formula, k is an integer of 5 to 5000, j is an integer of 0 to 5000, Ar ¹ and Ar ⁴ are the same or different divalent aromatic hydrocarbon groups, and Ar ² and Ar ³ are the same or different and are substituted or not. It represents a substituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. X is an aliphatic divalent group, a cycloaliphatic divalent group, or (Here, R ¹ and R ² are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, and 1 and m are each independently 0 to 4 Is an integer, Y is a single bond, 1 to 12 carbon atoms
A linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, embedded image Z represents a divalent group of an aliphatic hydrocarbon, and a
Is an integer of 0 to 20, b is an integer of 1 to 2000, R ³ , R ⁴
Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ) Is represented. ] 3. The electrophotographic photoreceptor according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (IV). [Chemical 7] [In the formula, n, Ar ² , Ar ³ and X have the same meanings as in claim 1.] 4. The aromatic polycarbonate resin comprises repeating units represented by the following general formulas (V) and (III), and the composition ratio of the repeating units is 0 <k / (k + j) ≦ 1.
The photoconductor for electrophotography according to claim 2, which is an aromatic polycarbonate resin. Embedded image [In the formula, k, j, Ar ² , Ar ³ and X have the same meanings as in claim 2]