JP3549350B2 - Electrophotographic photoreceptor - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an electrophotographic photoconductor, and more particularly, to a highly sensitive and highly durable electrophotographic photoconductor containing an aromatic polycarbonate resin having a charge transporting ability in a photosensitive layer.
[0002]
[Prior art]
In recent years, organic photoconductors (OPCs) have been widely used in copiers and printers. As a typical configuration example of the organic photoconductor, there is a laminated photoconductor in which a charge generation layer (CGL) and a charge transport layer (CTL) are sequentially stacked on a conductive substrate. The charge transport layer is formed from a low molecular charge transport material (CTM) and a binder resin. However, due to the inclusion of the low-molecular charge transport material, the mechanical strength inherent in the binder resin is reduced, which causes wear, scratches, cracks, etc. of the photoconductor, and impairs the durability of the photoconductor. Has become.
[0003]
As a photoconductive polymer material, vinyl polymers such as polyvinyl anthracene, polyvinyl pyrene, and poly-N-vinyl carbazole have been studied as charge transfer complex type photoconductors in the old days. Did not. On the other hand, in order to improve the above-mentioned drawbacks of the laminated photoreceptor, studies have been made on a polymer material having a charge transporting ability. For example, an acrylic resin having a triphenylamine structure [M. Stolka et al, J. Mol. Polym. Sci. , Vol 21, 969 (1983)], a vinyl polymer having a hydrazone structure (Japan HardCopy '89 P.67), and a polycarbonate resin having a triarylamine structure (U.S. Patent Nos. 4,801,517 and 4,806,443). Nos. 4,806,444, 4,937,165, 4,959,288, 5,030,532, 5,034,296, and 5,080,989 Specification, JP-A-64-9964, JP-A-3-221522, JP-A-2-304456, JP-A-4-11627, JP-A-4-175337, JP-A-4-18371, JP-A-4-184 No. 31404, JP-A-4-133065), but have not been put to practical use.
[0004]
M. A. Have compared the low molecular weight dispersion type with the polymerized polycarbonate using a tetraarylbenzidine derivative as a model compound, but have found that the polymer system has an order of magnitude lower drift mobility [ Physical Review B46 6705 (1992)]. Although the cause is not clear, it suggests that although the mechanical strength is improved by polymerizing, there is a problem in electrical characteristics such as sensitivity and residual potential.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described prior art, and by using an aromatic polycarbonate resin having a charge transport ability, to provide a highly sensitive and highly durable electrophotographic photoconductor, With that purpose.
[0006]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that on a conductive support, a novel aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formulas (II) and (III) The inventors have found that the above-mentioned problems can be solved by providing a photosensitive layer containing a novel aromatic polycarbonate resin composed of units as an active ingredient, and arrived at the present invention.
That is, the present invention includes the following (1) to (6).
[0007]
(1) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I).
[0008]
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[0009]
Wherein n is an integer of 5-5000, Ar¹And Ar⁵Is a divalent group of the same or different aromatic hydrocarbon, or a divalent group of the same or different heterocyclic ring,², Ar³, Ar⁴And Ar⁶Represents 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
[0010]
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[0011]
Where R¹And R²Are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m are each independently an integer of 0 to 4, Y is a single bond, A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO₂−,
[0012]
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[0013]
Z is a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, R is³, R⁴Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ]
(2) An aromatic polycarbonate resin comprising repeating units represented by the following general formulas (II) and (III) on a conductive support and having a composition ratio of the repeating units of 0 <k / (k + j) ≦ 1 is effective. An electrophotographic photoreceptor comprising a photosensitive layer containing a component.
[0014]
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[0015]
[In the formula, k is an integer of 5-5000, j is an integer of 0-5000, Ar¹And Ar⁵Is a divalent group of the same or different aromatic hydrocarbon, or a divalent group of the same or different heterocyclic ring,², Ar³, Ar⁴And Ar⁶Represents 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
[0016]
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[0017]
Where R¹And R²Are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a halogen atom, l and m are each independently an integer of 0 to 4, Y is a single bond, A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-, -SO₂−,
[0018]
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[0019]
Z is a divalent group of an aliphatic hydrocarbon, a is an integer of 0 to 20, b is an integer of 1 to 2000, R is³, R⁴Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon group. ]
(3)The aromatic polycarbonate resin isThe photoconductor for electrophotography according to the above (1), which is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (IV).
[0020]
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[0021]
[Wherein, n, Ar²~ Ar⁴And Ar⁵, X are as defined in claim 1]
(4)The aromatic polycarbonate resin isThe electrophotography according to the above (2), which is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formulas (V) and (III), wherein the repeating unit has a crude ratio of 0 <k / (k + j) ≦ 1. Photoreceptor.
[0022]
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[0023]
[Where k, j, Ar²~ Ar⁴And Ar⁶, X are as defined in the above (2)]
(5)The aromatic polycarbonate resin isThe electrophotographic photosensitive member according to the above (1), which is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (VI).
[0024]
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[0025]
[Wherein, n, Ar², Ar⁶, X are as defined in the above (1), R⁵And R⁶Is each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom, and r and s are each independently an integer of 0 to 4. ]
(6)The aromatic polycarbonate resin isAn electrophotographic polycarbonate resin according to the above (2), which is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formulas (VII) and (III), wherein the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1. Photoconductor.
[0026]
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[0027]
[Where k, j, Ar², Ar⁶, X have the same meaning as in the above (2). R⁵, R⁶, R, s are as defined in claim 5. ]
As described above, the electrophotographic photoreceptor of the present invention comprises an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (I) having a tertiary amino group in a photosensitive layer, or a tertiary amino group. Containing an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (II) and a repeating unit represented by the general formula (III), wherein the aromatic polycarbonate resin has a charge transporting ability. In addition, since the photoreceptor has high mechanical strength, the photoreceptor has high sensitivity and high durability. Hereinafter, the present invention will be described in more detail.
[0028]
As described above, the electrophotographic photoreceptor of the present invention comprises an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (I), (IV) or (VI) in a photosensitive layer or the general formula (II), It contains an aromatic polycarbonate resin comprising a repeating unit represented by (V) or (VII) and a repeating unit represented by the general formula (III). These aromatic polycarbonate resins are novel substances. It is manufactured by the following method.
[0029]
The aromatic polycarbonate resin of the present invention can be produced by a conventional method for producing a polycarbonate resin in the same manner as the known polymerization of bisphenol and a carbonic acid derivative. That is, the aromatic polycarbonate resin having a tertiary amino group-containing repeating unit represented by the general formula (II) (V) or (VII) used in the present invention is represented by the following general formula (VIII), (IX) or A diol compound having a tertiary amino group represented by (X) and a transesterification method with a bisaryl carbonate, a phosgene method by solution or interfacial polymerization with phosgene, or a bischloroformate derived from a diol is used. It is produced by a bischloroformate method or the like. At this time, a diol represented by the following general formula (XI) is used in combination to form a repeating unit having a tertiary amino group represented by the above general formula (II) and a repeating unit represented by the above general formula (III) An aromatic polycarbonate resin, an aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by the general formula (V) and a repeating unit represented by the general formula (III), or a compound represented by the general formula (VII) An aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by the formula (III) and a repeating unit represented by the general formula (III) can be produced, whereby an aromatic polycarbonate resin having desired properties can be produced. Is obtained. The proportion of the repeating unit having a tertiary amino group represented by the general formula (II) to the repeating unit represented by the general formula (III), and having the tertiary amino group represented by the general formula (V) The ratio of the repeating unit represented by the general formula (III) and the proportion of the repeating unit represented by the general formula (VII) and the repeating unit represented by the general formula (III) is selected from a wide range depending on desired properties. can do.
[0030]
The aromatic polycarbonate resin comprising a repeating unit having a tertiary amino group represented by the above general formula (I), (IV) or (VI) can be obtained by the following general formula (VIII), (IX) or (X) Can be obtained by interfacial polymerization or solution polymerization of a diol compound having a tertiary amino group represented by the following formula and a bischloroformate derived from the following general formula (XI). Further, a bischloroformate derived from a diol compound having a tertiary amino group represented by the general formula (VIII), (IX) or (X) is polymerized with a diol represented by the general formula (XI). Is also obtained.
[0031]
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[0032]
HO-X-OH (XI)
[Ar in each formula¹~ Ar⁶, R⁵, R⁶, R, s, and X are the same as in the previous meaning. ]
Hereinafter, the manufacturing method will be described in more detail.
[0033]
In the transesterification method, a diol compound and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C. under reduced pressure. The degree of reduced pressure is changed stepwise, and finally, the phenols formed are reduced to 1 mmHg or less to be distilled out of the system. The reaction time is usually about 1 to 4 hours. Further, if necessary, a molecular weight regulator and an antioxidant may be added. Examples of the bisaryl carbonate include diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.
[0034]
In the phosgene method, the reaction is usually performed in the presence of a deoxidizing agent and a solvent. As the deoxidizing agent, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene is used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and it is desirable to use a terminal stopper such as phenol or p-tert-butylphenol as a molecular weight regulator. The reaction temperature is usually from 0 to 40 ° C., the reaction time is from several minutes to 5 hours, and the pH during the reaction is preferably preferably maintained at 10 or more.
[0035]
When bischloroformate is used, it can be obtained by dissolving a diol compound in a solvent, adding a deoxidizing agent, and adding bischloroformate thereto. Tertiary amines such as trimethylamine, triethylamine and tripropylamine and pyridine are used as deacidifiers. As the solvent used in the reaction, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane are preferable. Further, it is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to 5 hours.
[0036]
Additives such as an antioxidant, a light stabilizer, a heat stabilizer, a lubricant, and a plasticizer can be added to the aromatic polycarbonate resin produced according to the above method, if necessary.
Hereinafter, the aromatic polycarbonate resin used in the present invention will be described in more detail.
[0037]
The aromatic polycarbonate resin used in the present invention is a homopolymer comprising a repeating unit represented by the above general formula (II), (V) or (VII), or the above general formula (I), (IV) or (VI) And an alternating copolymer comprising a repeating unit represented by the general formulas (II) and (III), the general formulas (V) and (III), or the general formulas (VII) and (III) Any of a random or block copolymer having a repeating unit as a constitutional unit may be used.
The molecular weight of the aromatic polycarbonate resin used in the present invention is 1,000 to 1,000,000, preferably 5000 to 5,000,000 in terms of polystyrene-equivalent number average molecular weight.
[0038]
Ar of each general formula¹And Ar⁵Represents a divalent group of an aromatic hydrocarbon group or a heterocyclic group, and specific examples thereof include benzene, naphthalene, biphenyl, terfel, pyrene, fluorene, 9,9-dimethylfluorene, thiophene, and the like as aromatic hydrocarbon groups. A divalent group such as benzothiophene, furan, benzofuran, carbazole and the like and a divalent group such as a diphenylether group and a diphenylthioether group in which two aryl groups are bonded by oxygen and sulfur. These aromatic hydrocarbons or heterocyclic groups may have an alkyl group, an alkoxy group and a halogen atom described later as substituents.
[0039]
Ar in each general formula², Ar³, Ar⁴And Ar⁶Represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group, and specific examples thereof include the following.
[0040]
Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, and the like, 5H-dibenzo [a, d] cycloheptenyl, and heterocyclic ring as an aromatic hydrocarbon group Examples of the group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, and a carbazolyl group. These aryl groups may have a substituent described later.
[0041]
R in each general formula¹, R², R⁵And R⁶Is a hydrogen atom, a halogen atom, an alkoxy group, an aromatic hydrocarbon group, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstitutedAromatic hydrocarbonThis represents a group, and specific examples thereof include those described below.
[0042]
(1) A halogen atom.
(2) an alkyl group; preferably C₁~ C₁₂Especially C₁~ C₈And more preferably C₁~ C₄Is a straight-chain or branched-chain alkyl group. These alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group,₁~ C₄An alkoxy group, a phenyl group, or a halogen atom, C₁~ C₄Alkyl group or C₁~ C₄May contain a phenyl group substituted with an alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 2-hydroxyethyl , 2-cyanoethyl, 2-ethoxyethyl, 2-methoxyethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl and the like.
[0043]
(3) alkoxy group (-OR⁷); R⁷Represents an alkyl group defined in the above (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyanoethoxy Group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.
Specific examples of the diol compound represented by the general formula (XI) are shown below.
[0044]
1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3- Aliphatic diols such as propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene ether glycol; And cycloaliphatic diols such as cyclohexanediol, 1,3-cyclohexanediol and cyclohexane-1,4-dimethanol.
[0045]
Examples of the diol having an aromatic ring include 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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) propa , 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 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-Hide Kishifeniru) - tetramethyldisiloxane, phenol-modified silicone oils.
1 to 6 are sectional views of the photoreceptor of the present invention.
[0046]
In the photoreceptor of the present invention, one or more of the above-mentioned aromatic polycarbonate resins are used in the photosensitive layer 2 (2 ′, 2 ″, 2 ′ ″, 2 ″ ″, 2 ′ ″ ″). ), But can be used as shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5, or FIG.
[0047]
The photoreceptor in FIG. 1 has a conductive support 1 on which a photosensitive layer 2 made of a sensitizing dye and an aromatic polycarbonate resin, and in some cases, a binder (binder resin) is provided. The aromatic polycarbonate resin here acts as a photoconductive substance, and the generation and movement of charge carriers required for light attenuation are performed via the aromatic polycarbonate resin. However, aromatic polycarbonate resins have almost no absorption in the visible region of light, so for the purpose of forming an image with visible light, sensitize by adding a sensitizing dye having absorption in the visible region. There is a need.
[0048]
The photoreceptor shown in FIG. 2 comprises a conductive support 1 on which a photosensitive layer 2 'in which a charge generation material 3 is dispersed in a charge transport medium 4 made of an aromatic polycarbonate resin alone or in combination with a binder is provided. It is. The aromatic polycarbonate resin here alone or in combination with a binder forms a charge transport medium, while the charge generating substance 3 (a charge generating substance such as an inorganic or organic pigment) generates a charge carrier. 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. In this photoreceptor, the basic condition is that the charge generation substance and the aromatic polycarbonate resin do not overlap each other mainly in the visible wavelength region. This is because light must be transmitted to the surface of the charge generation material 3 in order to efficiently generate charge carriers in the charge generation material 3. The aromatic polycarbonate resin represented by the repeating unit of the general formula (I) has almost no absorption in the visible region, and generally absorbs light in the visible region, and is particularly effective when combined with the charge generating substance 3 which generates a charge carrier. Its feature is that it works as a charge transport material. Note that a low-molecular charge transport material may be used in the charge transport medium 4.
[0049]
The photosensitive member shown in FIG. 3 is provided with a photosensitive layer 2 ″ comprising a laminate of a charge generating layer 5 mainly composed of a charge generating substance 3 and a charge transporting layer 4 containing an aromatic polycarbonate resin on a conductive support 1. It was done. In this photoreceptor, the light transmitted through the charge transport layer 4 reaches the charge generation layer 5 where charge carriers are generated, while the charge transport layer 4 receives charge carriers and transports them. The generation of charge carriers required for light attenuation is performed by the charge generating substance 3, and the transport of charge carriers is performed by the charge transport layer 4. Such a mechanism is the same as that described for the photoconductor shown in FIG.
[0050]
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 order to increase the charge generation efficiency, the charge generation layer 5 may contain the aromatic polycarbonate resin of the present invention. For the same purpose, a low molecular charge transport material may be used in the photosensitive layer 2 ''. The same applies to photosensitive layers 2 '' '' to 2 '' '' '' described later.
[0051]
The photoreceptor in FIG. 4 has a protective layer 6 provided on the charge transport layer 4. In the case of this configuration, a protective layer is formed on the charge transport layer 4 in combination with the aromatic polycarbonate resin of the present invention or a binder. As a matter of course, the formation on the low-molecular-weight-dispersion type charge transporting layer, which has been widely used, is effective. Note that a protective layer may be similarly provided on the photosensitive layer 2 'shown in FIG.
[0052]
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 the aromatic polycarbonate resin in FIG. 3, and the mechanism of generation and transport of the charge carriers is as described above. You can do the same. In this case, a protective layer 6 can be provided on the charge generation layer 5 as shown in FIG. 6 in consideration of mechanical strength.
In order to actually produce the photoreceptor of the present invention, if the photoreceptor shown in FIG. 1 is used, one or two or more aromatic polycarbonate resins are dissolved together with a binder and then further dissolved. A liquid containing an infectious agent may be prepared, applied to the conductive support 1 and dried to form the photosensitive layer 2.
[0053]
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, and 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. It is. Examples of sensitizing charges include triarylmethane dyes such as brilliant green, Victoria Blue B, methyl violet, crystal violet, and acid violet 6B, rhodamine B, rhodamine 6G, rhodamine G extra, eosin S, erythrosin, rose bengal, and fluorescein. Xanthene dyes, thiazine dyes such as methylene blue, and cyanine dyes such as cyanine.
[0054]
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 used in combination and dissolved, and this is used as a conductive material. What is necessary is just to apply | coat on the support body 1, and to dry and to form the photosensitive layer 2 '.
[0055]
The thickness of the photosensitive layer 2 'is 3 to 50 m, preferably 5 to 20 m. The amount of the tertiary amine compound in the photosensitive layer 2 'is 40 to 100% 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. % By weight. Examples of the charge generating substance 3 include inorganic pigments such as selenium, selenium-tellurium, cadmium sulfide, cadmium sulphide-selenium, and α-silicon, and examples of the organic pigments include CI Pigment Blue 25 (color index CI21180) and CI Pigment Red 41 ( CI2200), CI Acid Red 52 (CI45100), CI Basic Red 3 (CI45210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033), and an azo pigment having a distyrylbenzene skeleton (JP-A- JP-A-53-133445), azo pigments having a triphenylamine skeleton (described in JP-A-53-132347), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), oxadiazo Azo pigments having a fluorenone skeleton (described in JP-A-54-22834) and azo pigments having a bisstilbene skeleton (described in JP-A-54-22834). -17733), azo pigments having a distyryloxadiazole skeleton (described in JP-A-54-2129), and azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967). Azo pigments such as C.I. Pigment Blue 16 (CI74100); indigo-based pigments such as C.I.Bat Brown 5 (CI73410); C.I.Bad Dye (CI73030); Argo Scarlet B (manufactured by Bayer AG); Pens such as Indance Scarlet R (Bayer) Rylene pigments and the like can be mentioned. These charge generation substances may be used alone or in combination of two or more.
[0056]
Further, to prepare the photoreceptor shown in FIG. 3, a charge generating substance is vacuum-deposited on the conductive support 1, or the fine particles 3 of the charge generating substance are optionally dissolved in a suitable solvent in which a binder is dissolved. The dispersed liquid dispersion is applied and dried, or, if necessary, the surface is finished by a method such as buffing or the like, and the film thickness is adjusted to form the charge generating layer 5. The charge transport layer 4 may be formed by applying and drying a solution in which the above-described aromatic polycarbonate resin or the binder is used in combination.
Here, the charge generation material used for forming the charge generation layer 5 is the same as that described for the photosensitive layer 2 '.
[0057]
The thickness of the charge generation layer 5 is 5 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer 4 is 3 to 50 μm, preferably 5 to 20 μm. In the type in which the charge generation layer 5 has the fine particles 3 of the charge generation layer material dispersed in a binder, the ratio of the fine particles 3 of the charge generation material to the charge generation layer 5 is preferably 10 to 100% by weight. 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 charge transporting substance. Examples of the charge transporting substance used here include the following.
[0058]
Oxazole derivatives, oxadiazole derivatives (described in JP-A-52-139065 and JP-A-52-139066), imidazole derivatives, triphenylamine derivatives (described in JP-A-3-285960), and benzidine derivatives (described in Tokubo Shoko) 58-32372), α-phenylstilbene derivatives (described in JP-A-57-73075), and hydrazone derivatives (JP-A-55-154555, 55-156954, 55-52063). JP-A-56-81850), triphenylmethane derivatives (described in JP-B-5-10983), anthracene derivatives (described in JP-A-51-94829), styryl derivatives (described in JP-A-56-94829). -29245, 58-98043), carbazole derivatives Described in JP 58-58552 JP), pyrene derivatives (described in JP-A-2-94812).
[0059]
To prepare the photoreceptor shown in FIG. 4, the aromatic polycarbonate resin of the present invention is dissolved or applied alone or in combination with a binder on the photoreceptor shown in FIG. 6 are provided. The thickness of the protective layer is preferably from 0.15 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.
[0060]
In order to prepare the photoreceptor shown in FIG. 5, a solution in which an aromatic polycarbonate resin or a binder is dissolved and used in combination 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 of fine particles of the charge generation layer material in a solvent in which a binder is dissolved as required on the transport layer by a method such as spray coating and drying. The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG.
[0061]
By forming the above-mentioned protective layer 6 on the charge generation layer 5 of the photoreceptor thus obtained, the photoreceptor shown in FIG. 6 can be produced.
In the production of any of these photoconductors, a metal plate or a metal foil such as aluminum, a plastic film on which a metal such as aluminum is deposited, or a paper subjected to a conductive treatment is used for the conductive support 1.
[0062]
As the binder, polyamide, polyurethane, polyester, epoxy resin, polyketone, condensation resin such as polycarbonate, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, vinyl polymers such as polyacrylamide, etc. are used, All insulating and adhesive resins can be used. If necessary, a plasticizer is added to the binder. Examples of such a plasticizer include halogenated paraffin, dimethylnaphthalene, and dibutylphthalate. If necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer and a lubricant can be added.
[0063]
Further, the photosensitive member 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, and aluminum oxide, and the thickness is preferably 1 μm or less.
To make a copy using the photoreceptor of the present invention, the photosensitive surface is charged and exposed, developed, and then transferred to paper or the like as necessary.
The photoreceptor of the present invention has high sensitivity and excellent durability.
[0064]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described 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.
[0065]
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[0066]
4. N ′, N ″ -diphenyl-N ′, N ″ -bis (4-hydroxyphenyl) -1,4-bis (α-phenylstyryl) benzene-4 ′, 4 ″ -diamine in 40 ml of dry THF. 92 g (0.00739 mol) and 2.12 g (0.007 × 3 mol) of triethylamine were dissolved. A solution prepared by dissolving 1.70 g (0.00735 mol) of diethylene glycol bischloroformate in 8 ml of dry THF was added dropwise to the solution over 80 minutes while cooling with water. After completion of the dropwise addition, the viscous mixture was further stirred for 80 minutes, and 0.8 g of a 4 wt% phenol / dry THF solution was added. After stirring for 60 minutes, the resulting viscous mixture was precipitated in methanol, and the crude product was collected by filtration. This was subjected to two treatments of THF dissolution and methanol precipitation, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 1). The obtained target product was 5.49 g and the yield was 81.82%. The Tg point was 122.5 ° C.
[0067]
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[0068]
When the molecular weight of the obtained resin was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.
Number average molecular weight 3.40 × 10⁴
Weight average molecular weight 16.13 × 10⁴
In addition, in the infrared absorption spectrum (film) of this product, 1760 cm^-1The carbonate C =OAbsorption based on stretching vibration was observed. The results of elemental analysis are shown below.
[0069]
Elemental analysis value
Production Examples 2 to 11
Aromatic polycarbonate resins (Nos. 2 to 11) shown in Table 1 were obtained in the same manner as in Production Example 1.
[0070]
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[0071]
[Table 1]
[0072]
[Table 2]
[0073]
Production Example 12
1.60 g (0.002 mol) of N ′, N ″ -diphenyl-N ′, N ″ -bis (4-hydroxyphenyl) -1,4-bis (α-phenylstyryl) benzene-4 ′, 4 ″ -diamine Was placed in a reaction vessel, and an aqueous solution obtained by dissolving 0.32 g (0.002 × 4 mol) of sodium hydroxide in 30 ml of ion-exchanged water was added thereto, followed by stirring, and 0.356 g (0.002 × 0.6 mol) of triphosgene under ice-cooling. A solution dissolved in 10 ml of methylene chloride was slowly added dropwise over 20 minutes, 5 ml of methylene chloride was added while rinsing the vessel, and 0.1 g (0.025 mol) of sodium hydroxide was added at room temperature. Was added, and the mixture was stirred for 2 hours.The resulting viscous mixture was washed with a 5% aqueous sodium hydroxide solution, a 2% aqueous hydrochloric acid solution, and ion-exchanged water. After that, the precipitate was collected by reprecipitation in methanol, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 12) having the following structure: 1.25 g of the desired product was obtained at a yield of 75.3%. The glass transition temperature was 201.5 ° C.
[0074]
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[0075]
When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.
Weight average molecular weight 18.3 × 10⁴
Number average molecular weight 2.33 × 10⁴
In addition, the infrared absorption spectrum of this product was 1760 cm^-1The carbonate C =OAbsorption based on stretching vibration was observed. The results of elemental analysis are shown below.
[0076]
Elemental analysis value
Production Examples 13 and 14
In the same manner as in Production Example 12, the following aromatic polycarbonate resins (No. 13 and No. 14) were obtained.
[0077]
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[0078]
Production Example 15
4. N ′, N ″ -bis (4-methylphenyl) -N ′, N ″ -bis (4-hydroxyphenyl) -1,4-bis (α-phenylstyryl) benzene-4 ′, 4 ″ -diamine 14 g (0.006 mol) and 1.54 g (0.006 mol) of bisphenol C were put in a reaction vessel, and an aqueous solution in which 1.92 g (0.006 × 4 × 2 mol) of sodium hydroxide was dissolved in 800 ml of ion-exchanged water was added and stirred. Under ice cooling, a solution of 2.14 g (0.002 × 0.6 mol) of triphosgene dissolved in 500 ml of methylene chloride was slowly added dropwise over 60 minutes, and 100 ml of methylene chloride was added while rinsing the container. Then, 0.6 g of NaOH was added, a drop of triethylamine was added, and the mixture was stirred for 5 hours. After washing with an aqueous solution of sodium hydroxide, a 2% aqueous solution of hydrochloric acid and ion-exchanged water, the precipitate was reprecipitated in methanol, and the precipitate was collected by filtration and dried to obtain a polycarbonate resin (No. 15) having the following structure. The product was 5.11 g, the yield was 73.1%, and the glass transition temperature was 182.6 ° C.
[0079]
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[0080]
When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows.
Weight average molecular weight 22.5 × 10⁴
Number average molecular weight 1.53 × 10⁴
In the infrared absorption spectrum of this substance, 1760 cm^-1The carbonate C =OAbsorption based on stretching vibration was observed. The results of elemental analysis are shown below.
[0081]
Elemental analysis value
Production Examples 16-17
In the same manner as in Production Example 15, the following aromatic polycarbonate resins (No. 16 and No. 17) were obtained.
[0082]
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[0083]
Examples are shown below. In the examples, the aromatic polycarbonate resin No. 1 of the present invention was used. Is the above resin No. Corresponding to
[0084]
Example 1
A solution of polyamide resin (CM-8000: manufactured by Toray Industries, Ltd.) dissolved in a mixed solvent of methanol / butanol was applied on an aluminum plate with a doctor blade, and air-dried to form a 0.3 μm intermediate layer. A bisazo compound represented by the following formula as a charge generating material is pulverized by a ball mill in a mixed solvent of cyclohexanone and methyl ethyl ketone, and the obtained dispersion is applied with a doctor blade, and air-dried to about 1 μm. Was formed.
[0085]
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[0086]
Next, the polycarbonate resin No. obtained in Production Example 1 was used as a charge transport material. Was dissolved in dichloromethane, and this solution was applied on the charge generation layer with a doctor blade, air-dried, and then dried at 120 ° C. for 20 minutes to form a charge transport layer having a thickness of about 20 μm. . 1 was produced.
[0087]
Examples 2 to 15
Photoconductor No. 1 was operated in the same manner as in Example 1 except that the polycarbonate resin shown in the table was used instead of the polycarbonate resin (No. 1) used in Example 1. 2 to 15 were produced.
The photoreceptor No. Using a commercially available electrostatic copying paper tester (SP428, manufactured by Kawaguchi Electric Machinery Co., Ltd.) for 1 to 15, a corona discharge of -6 kV was performed in a dark place for 20 seconds to charge the surface._m(V) was measured and left in a dark place for another 20 seconds.₀(V) was measured. Then, a tungsten lamp light is applied so that the illuminance on the surface of the photoreceptor becomes 4.5 lux.₀(Seconds) until the value becomes 1/2, and the exposure amount E_1/2(Lux · sec) was calculated. Table 2 shows the results.
[0088]
[Table 3]
[0089]
Also, after charging each of the above photoreceptors using a commercially available electrophotographic copying machine, irradiating light through the original drawing to form an electrostatic latent image, and developing using a dry developer, the obtained The transferred image (toner image) was electrostatically transferred onto plain paper and fixed, and a clear transferred image was obtained. Similarly, when a wet type developer was used as the developer, a clear transfer image was obtained.
[0090]
【The invention's effect】
The electrophotographic photoreceptor of the present invention comprises an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (I) having a tertiary amine structure in a photosensitive layer, or the general formula (III) having a tertiary amine structure: It contains an aromatic polycarbonate resin consisting of a repeating unit represented by II) and a repeating unit represented by the general formula (III). These aromatic polycarbonate resins have charge transporting ability and high mechanical strength. , The photoreceptor has high sensitivity and high durability.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating an example of a layer configuration of an electrophotographic photosensitive member according to the present invention.
FIG. 2 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photoreceptor according to the present invention;
FIG. 3 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photoreceptor according to the present invention;
FIG. 4 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photoreceptor according to the present invention.
FIG. 5 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention;
FIG. 6 is a cross-sectional view showing another example of the layer configuration of the electrophotographic photosensitive member according to the present invention.
[Explanation of symbols]
1 conductive support
2,2 ', 2 ", 2"', 2 "', 2" "" photosensitive layer
3 charge generating substances
4 Charge transport layer or charge transport medium
5 charge generation layer
6 Protective layer

Claims (6)

An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing, as an active ingredient, an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I).
[In the formula, n is an integer of ^{5 to} 5000, Ar ¹ and Ar ⁵ are the same or different aromatic hydrocarbon divalent groups or the same or different heterocyclic divalent groups, and Ar ² , Ar ³ , Ar ⁴ and Ar ⁶ are the same or different and represent a substituted or unsubstituted 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 l and m are each independently an integer of 0 to 4. and, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O a -, - S -, - SO -, - SO 2 -,
Z represents an aliphatic hydrocarbon divalent group, a represents an integer of 0 to 20, b represents an integer of 1 to 2000, and R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group. Or a substituted or unsubstituted aromatic hydrocarbon group. ] An aromatic polycarbonate resin comprising a repeating unit represented by the following general formulas (II) and (III) on a conductive support, wherein the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1, is contained as an active ingredient. A photoconductor for electrophotography, wherein a photoconductive layer is provided.
[In the formula, k is an integer of 5 to 5000, j is an integer of 0 to 5000, Ar ¹ and Ar ⁵ are divalent groups of the same or different aromatic hydrocarbons, or divalent groups of the same or different heterocyclic rings. , Ar ² , Ar ³ , Ar ⁴ and Ar ⁶ 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
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 l and m are each independently an integer of 0 to 4. and, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O a -, - S -, - SO -, - SO 2 -,
Z represents an aliphatic hydrocarbon divalent group, a represents an integer of 0 to 20, b represents an integer of 1 to 2000, and R ³ and R ⁴ each independently represent a substituted or unsubstituted alkyl group. Or a substituted or unsubstituted aromatic hydrocarbon group. ] The electrophotographic photosensitive member 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).
[Wherein, n, Ar ^{2 to} Ar ⁴ and Ar ⁶ , X are as defined in claim 1] 3. The aromatic polycarbonate resin comprising a repeating unit represented by the following general formulas (V) and (III), wherein the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1. The electrophotographic photosensitive member according to the above.
[In the formula, k, j, Ar ^{2 to} Ar ⁴ and Ar ⁶ , X are as defined in claim 2] The electrophotographic photosensitive member according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (VI).
[In the formula, n, Ar ² , Ar ⁶ , and X have the same meanings as in claim 1. R ⁵ and R ⁶ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom, and r and s are each independently an integer of 0 to 4. . ] 3. The aromatic polycarbonate resin comprising a repeating unit represented by the following general formulas (VII) and (III), wherein the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1. The electrophotographic photosensitive member according to the above.
[In the formula, k, j, Ar ² , Ar ⁶ , and X have the same meaning as in claim 2. R ⁵ , R ⁶ , r, s are as defined in claim 5. ]