Electrophotographic photoconductor

BACKGROUND OF THE INVENTION

[0001] The present invention relates to an electrophotographic photoconductor (hereinafter also called “a photoconductor”). More specifically, the present invention relates to a photoconductor having a photosensitive layer formed on a conductive substrate, the photosensitive layer including charge generation substance, charge transport substance, and a binder resin. Such a photoconductor is useful for printers and copiers employing electrophotographic system.

[0002] A photoconductor, having a general structure of a conductive substrate and a photosensitive layer laminated on the substrate, exhibits a photoconductive function. A photoconductor called “an organic photoconductor” contains organic compounds as functional components serving for charge generation and charge transport. Particularly, a laminated-layer type organic photoconductor, laminating functional layers including a charge generation layer and a charge transport layer, has advantages, such as flexibility in material selection, easy design of performances, high productivity by use of coating process, and superior safety. Therefore, application of such organic photoconductors to various types of copiers and printers has been actively researched in recent years.

[0003] In particular, a system that uses hole-transport substance of a distyryl compound having a triphenylamine skeleton and a binder resin of polycarbonate for a hole-transport layer is expected to provide a photoconductor with high responsibility due to high hole mobility of the system. However, there was a problem of abrasion caused by mechanical stresses by image-transfer with light-exposure and by a blade for toner removal.

[0004] In recent years, organic photoconductors have remarkably developed in sensitivity and durability against repeated printings by virtue of inventions of charge generation materials and charge transport materials exhibiting excellent characteristics, as well as inventions of resins exhibiting high mechanical strength and favorable compatibility. Nevertheless, the known organic photoconductors are inferior in durability against repeated printings to photoconductors using inorganic materials of selenium and tellurium, as well as to photoconductors using amorphous silicon.

[0005] In order to solve the above problem, attempts to improve durability against repeated printings have been made by using polycarbonate with a large viscosity-average molecular weight. For example, the use of bisphenol A polycarbonate resin is disclosed in Japanese Unexamined Patent Application Publication (KOKAI) No. S62-160458, and the use of bisphenol Z polycarbonate resin is disclosed in Japanese Unexamined Patent Application Publication (KOKAI) No. H5-165230. However, technology has not yet been established that satisfies requirements for suppressing film-abrasion and for preventing “filming”, which is caused by the toner attached on the photoconductor surface.

OBJECTS AND SUMMARY OF THE INVENTION

[0006] It is an object of the present invention to provide an electrophotographic photoconductor which solves the foregoing problems.

[0007] It is a further object of the present invention to provide an electrophotographic photoconductor that exhibits minimal film-abrasion, as well as minimal probability of filming, and thus, high stability under repeated use for a long period of time, while retaining favorable characteristics of an organic photoconductor.

[0008] To solve the above problem, an electrophotographic photoconductor according to one embodiment of the present invention comprises a conductive substrate and a photosensitive layer on the substrate, the photosensitive layer containing charge generation substance, charge transport substance and a binder resin, wherein the binder resin has a dispersion d1, which indicates a range of molecular weight distribution of the resin and is defined by a ratio of z-average molecular weight Mz to weight-average molecular weight Mw, i.e., d1=Mz/Mw, is 1.6 or larger in a value converted to polystyrene standard.

[0009] An electrophotographic photoconductor according to another embodiment of the present invention comprises a conductive substrate and a photosensitive layer on the substrate, the photosensitive layer containing charge generation substance, charge transport substance and a binder resin, wherein the binder resin has a polydispersity d2, which also indicates a range of molecular weight distribution of the resin and is defined by a ratio of a weight-average molecular weight Mw to a number-average molecular weight Mn, i.e., d2=Mw/Mn, is 2.0 or larger in a value converted to polystyrene standard.

[0010] Advantageously, a polycarbonate resin may be used as the binder resin.

[0011] To solve the problem described earlier, the inventors of the present invention have made numerous studies and reached an idea, while not holding to any one particular theory, that giving the polymer of the binder resin a wide range of molecular weight and large overlapping formed by entanglement of principal chains of the polymer should be effective for improving abrasion resistance and also preventing filming of a photoconductor.

[0012] A synthetic polymer material is a collection of various species of molecules having different molecular weights. Mean values of the molecular weight differ each other depending on their calculation methods. There are three mean values of molecular weight: (1) a z-average molecular weight Mz averaged over z-values of each species of molecule, (2) a weight-average molecular weight Mw averaged over total weights of each species of molecule, and (3) a number-average molecular weight Mn simply averaged over molecular weights of each species of molecule. Precise definitions of these averages will be given later by equations (1), (2) and (3).

[0013] A collection of molecules consisting of molecules with wide range of molecular weight distribution has large difference between two averages of the three averages mentioned above. Namely, this kind of collection of molecules shows large difference between a z-average molecular weight and a weight-average molecular weight or large difference between a weight-average molecular weight and a number-average molecular weight. d1=Mz/Mw, a ratio of a z-average molecular weight to a weight-average molecular weight, is called dispersion and is an indicator of a range of molecular weight distribution. While, d2=Mw/Mn, a ratio of weight-average molecular weight to number-average molecular weight, is called polydispersity and is another indicator of a range of molecular weight distribution. Thus, the range of molecular weight distribution may be considered in terms of the dispersion d1 or the polydispersity d2.

[0014] The average values, a z-average molecular weight Mz, a weight-average molecular weight Mw, and a number-average molecular weight Mn, are defined by the following equations (1), (2) and (3), and actually obtained from a chromatogram of SEC (size exclusion chromatography) using the equations.

\begin{matrix} Mz = \frac{\sum (M_{i}^{3} N_{i})}{\sum (M_{i}^{2} N_{i})} = \frac{\sum (H_{i} M_{i}^{2})}{\sum (H_{i} M_{i})} & (1) \\ Mw = \frac{\sum (w_{i} M_{i})}{w} = \frac{\sum (M_{i}^{2} N_{i})}{\sum (M_{i} N_{i})} = \frac{\sum (H_{i} M_{i})}{\sum H_{i}} & (2) \\ Mn = \frac{w}{\sum N_{i}} = \frac{\sum (M_{i} N_{i})}{\sum N_{i}} = \frac{\sum H_{i}}{\sum (H_{i} / M_{i})} & (3) \end{matrix}

[0015] where “w” represents weight of the sample, “M”, a molecular weight, “N”, a number of molecules, “H”, height of chromatogram, and “i” represents i-th species of the polymer molecule and corresponds to i-th retention volume in the chromatography.

[0016] The inventors of the present invention have made studies on printing durability including abrasion and filming as well as coating characteristic, and have found that excellent printing durability and sensitivity characteristic are obtained by a photoconductor, in which the binder resin of the photosensitive layer of the photoconductor has dispersion d1=Mz/Mw of at least 1.6 or polydispersity d2=Mw/Mn of at least 2.0, where d1 and d2 are values converted to polystyrene standard. Mz is a z-average molecular weight, Mw, a weight-average molecular weight, and Mn, a number-average molecular weight. The present invention has been accomplished based on the finding. The inventors also found in the studies that this favorable effect is significant when polycarbonate is used as a binder resin.

[0017] In addition to the above effect, the wide range of molecular weight of the resin used in a photoconductor brings about an advantage in coating characteristic. If only a resin having a large value of a number-average molecular weight is used alone, such problems in coating process arise that viscosity is too large to facilitate coating operation and that the use of large amount of solvent causes excessive cooling of the photoconductor by large heat of vaporization in its drying process down to the temperature under a dew point resulting in dew condensation. Thus, high durability and ease of coating are in a trade-off relationship in conventional photoconductors This problem is solved by a resin having a range of molecular weight distribution larger than certain value according to the present invention.

[0018] The photoconductor of the present invention, even in repeated use for a long period of time, holds excellent electrophotographic characteristics, in particular, image reliability and stability in repeated use. The photoconductor of the present invention also may be applied to electrophotographic systems including a laser printer and an electrophotographic platemaking apparatus as well as a copier.

[0019] It has been confirmed that an actual electrophotographic system equipped with a photoconductor of the present invention does not cause deterioration of such characteristics as electric potential and sensitivity, even after a long period of time in service. Optical fatigue due to image exposure, mechanical stress due to rollers for charging and transfer and due to blades contacting with the photoconductor for toner removal, and thermal fatigue would cause abrasion and filming of the photoconductor. However, the abrasion and filming are effectively suppressed in a photoconductor of the present invention.

[0020] The above, and other objects, features and advantages of the present invention will become apparent from the following description read in conjunction with the accompanying drawings, in which like reference numerals designate the same elements.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021]
FIG. 1 is a schematic cross sectional view showing a negative-charging laminated-layer type photoconductor as one example of the present invention.

[0022]
FIG. 2 is a schematic cross sectional view showing a positive-charging laminated-layer type photo conductor as another example of the present invention.

[0023]
FIG. 3 is a schematic cross sectional view showing a positive-charging single-layer type photoconductor as still another example of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0024] Now, the invention will be described in greater detail with reference to certain aspects of preferred embodiments thereof and the accompanying drawings.

[0025] Referring to FIG. 1, the so-called negative-charging laminated-layer type photoconductor has a substrate 1 and a photosensitive layer 6 including a charge generation layer 2 and a charge transport layer 3.

[0026] Referring to FIG. 2, the so-called positive-charging laminated-layer type photoconductor has a substrate 1, a photosensitive layer 6 including a charge generation layer 2 and a charge transport layer 3, and a protective layer 4.

[0027] Referring to FIG. 3, the so-called positive-charging single layer type photoconductor has a substrate 1, a single photosensitive layer 5, and a protective layer 4. The protective layer is optionally provided. An intermediate layer, not shown in the figures, may be provided between the substrate and the photosensitive layer. While not being limited in scope, the invention will be described in detail with reference to a negative-charging laminated-layer type photoconductor.

[0028] Substrate 1 may be formed by an electrically conductive substrate alone, such as an aluminum cylindrical tube or an aluminum-deposited film, or such a substrate may have its surface treated to form anodized aluminum or to decorate with resin film.

[0029] Material of a polymer dispersion film used for the surface decoration of the conductive substrate may be selected from an insulative polymer, such as casein, poly(vinyl alcohol), nylon, polyamide, melamine or cellulose, a conductive polymer, such as polythiophene, polypyrrole or polyaniline, and these polymers to which metal oxide powder or low molecular weight compound is added.

[0030] Charge generation layer 2 includes charge generation substance and a binder resin. The charge generation substance may be selected from phthalocyanine compounds, azo compounds and derivatives of these compounds. Specific examples of the charge generation substances are shown by the chemical formulas (I-1) to (I-18).

[0031] The binder resin used in the charge generation layer may be selected from polycarbonate, polyester, polyamide, polyurethane, epoxy resin, poly(vinyl butyral), poly(vinyl acetal), phenoxy resin, silicone resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl formal, cellulose resin, copolymers of these substances, halide and cyanoethylate of these substances, and a mixture of these substances.

[0032] Charge transport layer 3 includes charge transport substance and a binder resin. The charge transport substance may be selected from hydrazone compounds, amine compounds, and appropriate combinations of these substances. Specific examples of the charge transport substances are shown by the chemical formulas (II-1) to (II-12).

[0033] The binder resin used in the charge transport layer may be selected from polycarbonate, polystylene, allyl resin, polyphenylene ether, and acrylic resin. Specific examples of the binder resin are shown by the chemical formulas (III-1) to (III-8). Polycarbonate is preferably used for the binder resin of the charge transport layer, although not limited to polycarbonate.

[0034] The binder resin for the charge transport layer of the photoconductor according to the present invention is prepared so that the dispersion d1, an indicator of a range of molecular weight distribution, is at least 1.6, or the polydispersity d2 is at least 2.0, where both d1 and d2 are values converted to polystyrene standard. A preferred result is obtained by a photoconductor in which the binder resin of the charge transport layer is prepared so that the dispersion d1 is in the range from 1.6 to 2.5 or the polydispersity d2 is in the range from 2.0 to 3.0.

[0035] The polycarbonate resins exemplified above may be synthesized by a known method, such as melt polycondensation through transesterification reaction or interface condensation of dicarboxylic acid chloride and alkali salt, to obtain a polycarbonate resin having desired dispersion or polydispersity of the molecular weight distribution.

[0036] The photoconductor may contain an antioxidant agent as an additive. The specific examples of the antioxidant agent are shown by the chemical formulas (IV-1) to (IV-45).

[0037] In the case the photoconductor is of a single-layer type, photosensitive layer 5 contains charge generation substance, charge transport substance and a binder resin, in which the binder resin is prepared so that the dispersion d1 or polydispersity d2, indicators of a range of molecular weight distribution, is in the range given above for the case of the laminated-layer type photoconductor. The material of the binder resin may also be selected from similar substances to those in the laminated-layer type photoconductor.

EXAMPLES

[0038] Although the present invention will be described in further detail in the following referring to specific examples of the embodiment thereof, the invention shall not be limited by the examples. The conductive substrate of every Example or Comparative Example in the following is an aluminum cylindrical tube having thickness of 1 mm, length of 310 mm and outer diameter of 60 mm. The cylindrical tube was used for a conductive substrate after cleaning and drying.

Example 1 (E1)

[0039] An intermediate layer was formed by dip-coating the surface of the above-described substrate with a coating liquid and dried at 90° C. for 30 min, to be a resin layer having thickness of 0.1 μm. The coating liquid for the resin film of the intermediate layer was prepared by dissolving 10 parts by weight of an alcohol-soluble copolymerized polyamide resin CM 8000 (manufactured by Toray Industries Co., Ltd.) into mixed solvent of 45 parts by weight of methanol and 45 parts by weight of methylene chloride.

[0040] Then, a charge generation layer having film thickness of 0.2 μm was formed by dip-coating the intermediate layer with a coating liquid followed by drying at 90° C. for 30 min. The coating liquid for the charge generation layer was prepared by mixing 1 part by weight of poly(vinyl acetal) resin S-LEC KS-1 (manufactured by Sekisui Chemical Co., Ltd.) and 1 part by weight of the bisazo compound of formula (I-17) as charge generation substance with 150 parts by weight of methylethyl ketone, and subjecting to dispersion treatment in a ballmill for 48 hrs.

[0041] Subsequently, a charge transport layer having thickness of 20 μm was formed by dip-coating the charge generation layer with a coating liquid followed by drying at 90° C. for 30 min. The coating liquid for the charge transport layer was prepared by dissolving a mixed material of 100 parts by weight of the diamine compound of the formula (II-7) as charge transport substance and 100 parts by weight of the bisphenol Z polycarbonate of the formula (III-2) as a resin binder, and 5 parts by weight of a hindered phenol compound of the formula (IV-9), in 700 parts by weight of dichloromethane. Here, this bisphenol Z polycarbonate had the values of average molecular weight and ratios between them of Mw=58,847, Mz=97,215, Mn=28,224, Mz/Mw=1.652, and Mw/Mn=2.085.

Example 2 (E2)

[0042] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol Z polycarbonate of the formula (III-2) that had the values: Mw=90,703, Mz=166,894, Mn=42,031, Mz/Mw=1.840, and Mw/Mn=2.157.

Example 3 (E3)

[0043] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol Z polycarbonate of the formula (III-2) that had the values: Mw=125,775, Mz=408,768, Mn=53,361, Mz/Mw=3.250, and Mw/Mn=2.375.

Example 4 (E4)

[0044] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol A polycarbonate of the formula (III-1) that had the values: Mw=55,659, Mz=90,724, Mn=24,354, Mz/Mw=1.630, and Mw/Mn=2.285.

Example 5 (E5)

[0045] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol A polycarbonate of the formula (III-1) that had the values: Mw=118,527, Mz=256,374, Mn=47,354, Mz/Mw=2.163, and Mw/Mn=2.503.

Example 6 (E6)

[0046] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of isophorone type polycarbonate of the formula (III-3) that had the values: Mw=64,030, Mz=114,166, Mn=31,950, Mz/Mw=1.783, and Mw/Mn=2.004.

Example 7 (E7)

[0047] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol C polycarbonate of the formula (III-4) that had the values: Mw=88,945, Mz=167,306, Mn=33,794, Mz/Mw=1.881, and Mw/Mn=2.632.

Example 8 (E8)

[0048] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of polycarbonate of the formula (III-5) that had the values: Mw=118,908, Mz=193,107, Mn=37,987, Mz/Mw 1.624, and Mw/Mn=3.130.

Example 9 (E9)

[0049] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-6) that had the values: Mw=107,046, Mz=276,285, Mn=35,072, Mz/Mw=2.581, and Mw/Mn=3.052.

Example 10 (E10)

[0050] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-7) that had the values: Mw=68,212, Mz=121,758, Mn=31,404, Mz/Mw=1.785, and Mw/Mn=2.017.

Example 11 (E11)

[0051] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-8) that had the values: Mw=156,578, Mz=367,958, Mn=41,423, Mz/Mw=2.350, and Mw/Mn=3.800.

Example 12 (E12)

[0052] A photoconductor was fabricated in the same manner as in Example 1 except that the charge generation substance was replaced by a metal phthalocyanine compound of the formula (I-3).

Example 13 (E13)

[0053] A photoconductor was fabricated in the same manner as in Example 1 except that the charge generation substance was replaced by a bisazo compound of the formula (I-7).

Example 14 (E14)

[0054] A photoconductor was fabricated in the same manner as in Example 1 except that the charge transport substance was replaced by a butadiene compound of the formula (II-4).

Example 15 (E15)

[0055] A photoconductor was fabricated in the same manner as in Example 1 except that the charge transport substance was replaced by a styryl compound of the formula (II-11).

Example 16 (E16)

[0056] A photoconductor was fabricated in the same manner as in Example 1 except that the antioxidant in the charge transport layer was replaced by a compound of the formula (IV-30).

Example 17 (E17)

[0057] A photoconductor was fabricated in the same manner as in Example 1 except that the antioxidant in the charge transport layer was replaced by a compound of the formula (IV-37).

Comparative Example 1 (CE1)

[0058] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol Z polycarbonate of the formula (III-2) that had the values: Mw=40,686, Mz=62,290, Mn=22,548, Mz/Mw=1.531, and Mw/Mn=1.804.

Comparative Example 2 (CE2)

[0059] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol Z polycarbonate of the formula (III-2) that had the values: Mw=60,845, Mz=93,580, Mn=38,028, Mz/Mw=1.538, and Mw/Mn=1.600.

Comparative Example 3 (CE3)

[0060] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol Z polycarbonate of the formula (III-2) that had the values: Mw=93,562, Mz=135,010, Mn=53,259, Mz/Mw=1.443, and Mw/Mn=1.757.

Comparative Example 4 (CE4)

[0061] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol A polycarbonate of the formula (III-1) that had the values: Mw=52,831, Mz=80,673, Mn=32,542, Mz/Mw=1.527, and Mw/Mn=1.623.

Comparative Example 5 (CE5)

[0062] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol A polycarbonate of the formula (III-1) that had the values: Mw=86,158, Mz=132,597, Mn=47,223, Mz/Mw=1.539, and Mw/Mn=1.825.

Comparative Example 6 (CE6)

[0063] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of isophorone type polycarbonate of the formula (III-3) that had the values: Mw=55,705, Mz=82,332, Mn=31,232, Mz/Mw=1.478, and Mw/Mn=1.783.

Comparative Example 7 (CE7)

[0064] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of bisphenol C polycarbonate of the formula (III-4) that had the values: Mw=54,789, Mz=83,772, Mn=33,129, Mz/Mw=1.529, and Mw/Mn=1.654.

Comparative Example 8 (CE8)

[0065] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of polycarbonate of the formula (III-5) that had the values: Mw=60,612, Mz=89,039, Mn=34,524, Mz/Mw=1.469, and Mw/Mn=1.756.

Comparative Example 9 (CE9)

[0066] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-6) that had the values: Mw=80,106, Mz=126,728, Mn=45,283, Mz/Mw=1.582, and Mw/Mn=1.769.

Comparative Example 10 (CE10)

[0067] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-7) that had the values: Mw=78,943, Mz=119,362, Mn=42,580, Mz/Mw=1.512, and Mw/Mn=1.854.

Comparative Example 11 (CE11)

[0068] A photoconductor was fabricated in the same manner as in Example 1 except that the resin binder of the charge transport layer was replaced by 100 parts by weight of copolymerized polycarbonate of the formula (III-8) that had the values: Mw=85,191, Mz=132,983, Mn=45,242, Mz/Mw=1.561, and Mw/Mn=1.883.

EVALUATION OF THE PHOTOCONDUCTORS

[0069] Evaluation of each of the Examples and Comparative Examples was conducted in terms of dispersion and polydispersity of the polycarbonate in the charge transport layer and characteristics of the photoconductor including an amount of abrasion, occurrence of filming, and dew condensation on the photoconductor surface.

[0070] The dispersion and polydispersity were measured by means of gel permeation chromatography (GPC). In the method, 100 μl of a solution prepared by dissolving 0.02 g of a specimen taken from the charge transport layer in 5 ml of tetrahydrofuran was injected into the column with flow velocity of 1 ml/min. The column temperature was set at 40° C. The GPC and the column used in the measurement were products of Waters Corporation, Mass., USA, and the polystyrene standard sample was “TSK standard” manufactured by TOSOH Corporation, Tokyo, Japan. The results of the evaluation are shown in Tables 1 through 5.

1TABLE 1specimenE1E2E3E4E5E6CTL binderIII-2III-2III-2III-1III-1III-3resin (*1)CG substanceI-17I-17I-17I-17I-17I-17(*2)CT substanceII-7II-7II-7II-7II-7II-7(*3)antioxidantIV-9IV-9IV-9IV-9IV-9IV-9Mw (*4)58,84790,703125,77555,659118,52764,030Mz (*5)97,215166,894408,76890,724256,374114,166Mn (*6)28,22442,03153,36124,35447,35431,950dispersion1.6521.8403.2501.6302.1631.783d1 (*7)polydispersity2.0852.1582.3572.2852.5032.004d2 (*8)abrasion0.91.10.70.90.81.0μm (*9)filmingAAAAAAdewaabaaacondensationTable entry in the ‘filming’ row,A: rarely occurredB: often occurredC: very frequently occurredTable entry in the ‘dew condensation’ row,a: little observedb: fairly observedC: very much observed(*1) binder resin in the charge transport layer(*2) charge generation substance(*3) charge transport substance(*4) weight-average molecular weight(*5) z-average molecular weight(*6) number-average molecular weight(*7) d1 = Mz/Mw(*8) d2 = Mw/Mn(*9) amount of abrasion after 10,000 sheets of printing

[0071]

2

TABLE 2

specimen
E7
E8
E9
E10
E11
E12

CTL binder
III-4
III-5
III-6
III-7
III-8
III-2

resin (*1)

CG substance
I-17
I-17
I-17
I-17
I-17
I-4

(*2)

CT substance
II-7
II-7
II-7
II-7
II-7
II-7

(*3)

antioxidant
IV-9
IV-9
IV-9
IV-9
IV-9
IV-9

Mw (*4)
88,945
118,908
107,046
68,212
156,578
58,847

Mz (*5)
167,306
193,107
276,285
121,758
367,958
97,215

Mn (*6)
33,794
37,987
35,072
31,404
41,423
28,224

dispersion
1.881
1.624
2.581
1.785
2.350
1.652

d1 (*7)

polydispersity
2.632
3.130
3.052
2.017
3.800
2.085

d2 (*8)

abrasion
0.9
0.8
0.9
0.8
0.7
1.0

μm (*9)

filming
A
A
A
A
A
A

dew
a
a
a
a
b
a

condensation

Table entry in the ‘filming’ row,

A: rarely occurred
B: often occurred
C: very frequently occurred

Table entry in the ‘dew condensation’ row,

a: little observed
b: fairly observed
C: very much observed

(*1) binder resin in the charge transport layer

(*2) charge generation substance

(*3) charge transport substance

(*4) weight-average molecular weight

(*5) z-average molecular weight

(*6) number-average molecular weight

(*7) d1 = Mz/Mw

(*8) d2 = Mw/Mn

(*9) amount of abrasion after 10,000 sheets of printing

[0072]

3

TABLE 3

specimen
E13
E14
E15
E16
E17

CTL binder resin (*1)
III-2
III-2
III-2
III-2
III-2

CG substance (*2)
I-7
I-17
I-17
I-17
I-17

CT substance (*3)
II-7
II-4
II-11
II-7
II-7

antioxidant
IV-9
IV-9
IV-9
IV-30
IV-37

Mw (*4)
58,847
58,847
58,847
58,847
58,847

Mz (*5)
97,215
97,215
97,215
97,215
97,215

Mn (*6)
28,224
28,224
28,224
28,224
28,224

dispersion d1 (*7)
1.652
1.652
1.652
1.652
1.652

polydispersity d2 (*8)
2.085
2.085
2.085
2.085
2.085

abrasion μm (*9)
0.8
0.9
0.8
1.0
0.9

filming
A
A
A
A
A

dew condensation
a
a
a
a
a

Table entry in the ‘filming’ row,

A: rarely occurred
B: often occurred
C: very frequently occurred

Table entry in the ‘dew condensation’ row,

a: little observed
b: fairly observed
C: very much observed

(*1) binder resin in the charge transport layer

(*2) charge generation substance

(*3) charge transport substance

(*4) weight-average molecular weight

(*5) z-average molecular weight

(*6) number-average molecular weight

(*7) d1 = Mz/Mw

(*8) d2 = Mw/Mn

(*9) amount of abrasion after 10,000 sheets of printing

[0073]

4

TABLE 4

specimen
CE1
CE2
CE3
CE4
CE5
CE6

CTL binder
III-2
III-2
III-2
III-1
III-1
III-3

resin (*1)

CG substance
I-17
I-17
I-17
I-17
I-17
I-17

(*2)

CT substance
II-7
II-7
II-7
II-7
II-7
II-7

(*3)

antioxidant
IV-9
IV-9
IV-9
IV-9
IV-9
IV-9

Mw (*4)
40,636
60,845
93,562
52,831
86,158
55,705

Mz (*5)
62,290
93,580
135,010
80,673
132,597
82,332

Mn (*6)
22,548
38,028
53,259
32,542
47,223
31,232

dispersion
1.531
1.538
1.443
1.527
1.539
1.478

d1 (*7)

polydispersity
1.804
1.600
1.757
1.623
1.825
1.783

d2 (*8)

abrasion
1.4
1.3
1.1
1.1
1.1
1.3

μm (*9)

filming
B
B
B
B
B
B

dew
a
b
b
a
b
a

condensation

Table entry in the ‘filming’ row,

A: rarely occurred
B: often occurred
C: very frequently occurred

Table entry in the ‘dew condensation’ row,

a: little observed
b: fairly observed
C: very much observed

(*1) binder resin in the charge transport layer

(*2) charge generation substance

(*3) charge transport substance

(*4) weight-average molecular weight

(*5) z-average molecular weight

(*6) number-average molecular weight

(*7) d1 = Mz/Mw

(*8) d2 = Mw/Mn

(*9) amount of abrasion after 10,000 sheets of printing

[0074]

5

TABLE 5

specimen
CE7
CE8
CE9
CE10
CE11

CTL binder resin (*1)
III-4
III-5
III-6
III-7
III-8

CG substance (*2)
I-17
I-17
I-17
I-17
I-17

CT substance (*3)
II-7
II-7
II-7
II-7
II-7

antioxidant
IV-9
IV-9
IV-9
IV-9
IV-9

Mw (*4)
54,789
60,612
80,106
78,943
85,191

Mz (*5)
83,772
89,039
126,728
119,362
132,983

Mn (*6)
33,129
34,524
45,283
42,580
45,242

dispersion d1 (*7)
1.529
1.469
1.582
1.512
1.561

polydispersity d2 (*8)
1.654
1.756
1.769
1.854
1.883

abrasion μm (*9)
1.3
1.2
1.3
1.1
1.0

filming
C
B
B
B
B

dew condensation
a
a
b
b
c

Table entry in the ‘filming’ row,

A: rarely occurred
B: often occurred
C: very frequently occurred

Table entry in the ‘dew condensation’ row,

a: little observed
b: fairly observed
C: very much observed

(*1) binder resin in the charge transport layer

(*2) charge generation substance

(*3) charge transport substance

(*4) weight-average molecular weight

(*5) z-average molecular weight

(*6) number-average molecular weight

(*7) d1 = Mz/Mw

(*8) d2 = Mw/Mn

(*9) amount of abrasion after 10,000 sheets of printing

[0075] As is apparent from Tables 1 through 5, excellent printing durability is obtained by a photoconductor using a binder resin so prepared that the dispersion d1=Mz/Mw is at least 1.6 or the polydispersity d2=Mw/Mn is at least 2.0, where each of d1 and d2 is in a value converted to polystyrene standard, and Mz, Mw and Mn, which indicate ranges of molecular weight distribution of the resin, are z-average molecular weight, weight-average molecular weight and number-average molecular weight, respectively.

[0076] Every photoconductor of Example 1 through Example 17, which uses polycarbonate with dispersion Mz/Mn of at least 1.6 or polydispersity Mw/Mn of at least 2.0, according to the present invention, showed little abrasion, rare filming, and scare dew condensation. That is to say, the photoconductor of the invention exhibits well-balanced characteristics.

[0077] In contrast, every photoconductor of Comparative Example 1 through Comparative Example 11, which uses polycarbonate with dispersion Mz/Mw of less than 1.6 or polydispersity Mw/Mn of less than 2.0, resulted in problems. Namely, when polycarbonate with small molecular weight is used, the amount of abrasion is relatively large. When polycarbonate with large molecular weight is used, while an amount of abrasion is relatively small, the coating process requires plenty of solvent, which raises dew condensation in the process of drying the coated surface of the photoconductor drum. Further, the photoconductors of Comparative Examples are generally liable to cause filming and abrasion, thus, don't exhibit well-balance characteristics.

[0078] It is further apparent that the photoconductors of Examples according to the invention commonly showed excellent resistance to abrasion and little occurrence of filming, which secure long life. The effect have been brought about by the use of the polycarbonate that has a range of molecular weight distribution larger than certain value, namely, dispersion d1=Mz/Mw of at least 1.6 or polydispersity d2=Mw/Mn of at least 2.0, where d1 and d2 are values converted to polystyrene standard. It should be noted that the effects have been attained in every Examples according to the invention irrespective of species of the polycarbonate, charge generation substance, charge transport substance, and antioxidant agent.

[0079] As described, the present invention provides a photoconductor that suppresses abrasion and filming in the operation for long periods, and also facilitates the coating process.

[0080] Having described preferred embodiments of the invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to those precise embodiments, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims.

Electrophotographic photoconductor

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