JP7338402B2 - Electrophotographic photoreceptor - Google Patents

Description

The present invention relates to an electrophotographic photoreceptor.

An electrophotographic photoreceptor is used as an image carrier in an electrophotographic image forming apparatus (for example, a printer or a multifunction machine). An electrophotographic photoreceptor has a photosensitive layer. As the electrophotographic photoreceptor, for example, a single-layer electrophotographic photoreceptor and a laminated electrophotographic photoreceptor are used. A single-layer electrophotographic photoreceptor includes a single-layer photosensitive layer having a charge generation function and a charge transport function. A laminated electrophotographic photoreceptor includes a photosensitive layer including a charge generation layer having a charge generation function and a charge transport layer having a charge transport function.

An example of Patent Document 1 describes the production of a polycarbonate copolymer using p-tert-butylphenol as a terminal terminator.

JP 2012-51983 A

However, the polycarbonate copolymer described in Patent Document 1 is insufficient in abrasion resistance.

The present invention has been made in view of the above problems, and an object thereof is to provide an electrophotographic photoreceptor which is excellent in abrasion resistance and also excellent in light resistance to white light.

The electrophotographic photoreceptor of the present invention comprises a conductive substrate and a photosensitive layer. The photosensitive layer includes a charge generation layer and a charge transport layer. The charge generation layer contains a charge generation agent. The charge transport layer contains a binder resin, an azo compound represented by general formula (30), and a hole transport agent. The content of the azo compound represented by the general formula (30) is 2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin. The binder resin comprises a polyarylate resin having at least one first repeating unit, at least one second repeating unit, and terminal groups. The first repeating unit is represented by general formula (1). The second repeating unit is represented by general formula (2). The terminal group is represented by general formula (3).

In general formula (30), R ¹¹ and R ¹² each independently represent an alkyl group having 1 or more and 3 or less carbon atoms. Ar ¹ and Ar ² each independently represent an arylene group having 6 to 14 carbon atoms which may be substituted with at least one substituent, and the substituent is an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. Q represents a monovalent group represented by general formula (Q1) or (Q2).

In general formula (Q1), Ar ³ and Ar ⁴ each independently represent an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms. * represents a bond. In general formula (Q2), Z represents a 6- to 18-membered heterocyclic ring having at least a nitrogen atom as a ring-constituting atom. * represents a bond.

In general formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ may combine with each other to represent a divalent group represented by general formula (X). In general formula (2), X ¹ represents a divalent group represented by chemical formula (2A), (2B), (2C), or (2D). In general formula (3), R ^f represents a chain aliphatic group having 1 or more and 20 or less carbon atoms substituted with one or more fluorine atoms.

In the general formula (X), t represents an integer of 1 or more and 3 or less. * represents a bond.

The electrophotographic photoreceptor of the present invention is excellent in wear resistance and light resistance to white light.

1 is a partial cross-sectional view of an electrophotographic photoreceptor according to an embodiment of the present invention; FIG. 1 is a partial cross-sectional view of an electrophotographic photoreceptor according to an embodiment of the present invention; FIG. 1 is a partial cross-sectional view of an electrophotographic photoreceptor according to an embodiment of the present invention; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is by no means limited to the following embodiments. The present invention can be implemented with appropriate modifications within the scope of the purpose of the present invention. It should be noted that descriptions of overlapping descriptions may be omitted as appropriate, but the gist of the invention is not limited.

In the following description, the compound name may be followed by "system" to collectively refer to compounds and their derivatives. In addition, when the name of a polymer is expressed by adding "system" to the name of a compound, it means that the repeating unit of the polymer is derived from the compound or its derivative.

Next, the substituents used in this specification are explained. an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 3 or more carbon atoms Each alkyl group of up to 5 is straight or branched and unsubstituted unless otherwise specified. Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1 -methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethyl butyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2 -trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl and 3-ethylbutyl groups, linear and branched heptyl groups, and linear and branched octyl groups. Examples of alkyl groups having 1 to 6 carbon atoms, alkyl groups having 1 to 4 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and alkyl groups having 3 to 5 carbon atoms are, respectively, Among the groups described as examples of the alkyl group having 1 to 8 carbon atoms, it is a group having the corresponding number of carbon atoms.

An alkoxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms are linear or branched unless otherwise specified. is unsubstituted. Examples of alkoxy groups having 1 to 8 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 1-ethylpropoxy group, 2-ethylpropoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, 2,2- dimethylpropoxy group, 1,2-dimethylpropoxy group, n-hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1- dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group, 3,3-dimethylbutoxy group, 1,1,2- trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethylbutoxy, 2-ethylbutoxy, 3-ethylbutoxy, linear and branched heptyloxy groups, and linear and A branched octyloxy group can be mentioned. Examples of the alkoxy group having 1 to 4 carbon atoms and the alkoxy group having 1 to 3 carbon atoms are each the corresponding carbon among the groups described as examples of the alkoxy group having 1 to 8 carbon atoms It is a group having the number of atoms.

Cycloalkanes having 5 to 7 carbon atoms are unsubstituted unless otherwise specified. Cycloalkanes having 5 to 7 carbon atoms include, for example, cyclopentane, cyclohexane, and cycloheptane.

Aryl groups having from 6 to 14 carbon atoms are unsubstituted unless otherwise specified. Examples of aryl groups having 6 to 14 carbon atoms include phenyl, naphthyl, indacenyl, biphenylenyl, acenaphthylenyl, anthryl and phenanthryl groups.

An arylene group having 6 to 14 carbon atoms and an arylene group having 6 to 10 carbon atoms are each unsubstituted unless otherwise specified. Examples of the arylene group having 6 to 14 carbon atoms include phenylene group, naphthalenediyl group, indacenediyl group, biphenylenediyl group, acenaphthylenediyl group, anthrylenediyl group, and phenanthenediyl group. Examples of the arylene group having 6 or more and 10 or less carbon atoms are groups having the corresponding number of carbon atoms among the groups described as examples of the arylene group having 6 or more and 14 or less carbon atoms.

6-18 membered heterocycles and 13-15 membered heterocycles are unsubstituted unless otherwise specified. These heterocyclic rings have at least a nitrogen atom as ring-constituting atoms, and may further have an oxygen atom and a carbon atom. 6-18 membered heterocycles include, for example, carbazole, indole, isoindole, indazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, purine, pteridine, phenanthridine, acridine, phenazine, phenanthroline, chemical formula A heterocyclic ring represented by (HC-1) and a heterocyclic ring represented by the chemical formula (HC-2) can be mentioned. Examples of the 13- to 15-membered heterocyclic ring are groups having the corresponding number of ring members among the heterocyclic rings described as examples of the 6- to 18-membered heterocyclic ring. The substituents used in the present specification have been described above.

<Electrophotographic photoreceptor>
The present embodiment relates to an electrophotographic photoreceptor (hereinafter sometimes referred to as a photoreceptor). The structure of the photoreceptor 1 of this embodiment will be described below with reference to FIGS. 1 to 3. FIG. 1 to 3 each show a partial cross-sectional view of photoreceptor 1. FIG.

As shown in FIG. 1, the photoreceptor 1 includes a conductive substrate 2 and a photosensitive layer 3. As shown in FIG. The photosensitive layer 3 includes a charge generation layer 3a and a charge transport layer 3b. That is, the photoreceptor 1 is provided with the charge generation layer 3a and the charge transport layer 3b as the photosensitive layer 3. As shown in FIG. Photoreceptor 1 is a laminated electrophotographic photoreceptor.

As shown in FIG. 1, a charge generation layer 3a may be provided on the conductive substrate 2, and a charge transport layer 3b may be provided on the charge generation layer 3a. As shown in FIG. 2, the photoreceptor 1 may have a charge transport layer 3b provided on the conductive substrate 2 and a charge generation layer 3a provided on the charge transport layer 3b.

As shown in FIG. 3, the photoreceptor 1 may include a conductive substrate 2, a photosensitive layer 3, and an intermediate layer 4 (undercoat layer). An intermediate layer 4 is provided between the conductive substrate 2 and the photosensitive layer 3 . As shown in FIGS. 1 and 2, the photosensitive layer 3 may be provided directly on the conductive substrate 2 . Alternatively, as shown in FIG. 3, a photosensitive layer 3 (for example, a charge generation layer 3a or a charge transport layer 3b) may be provided on the conductive substrate 2 with an intermediate layer 4 interposed therebetween.

The photoreceptor 1 may comprise a conductive substrate 2, a photosensitive layer 3, and a protective layer (not shown). A protective layer is provided on the photosensitive layer 3 .

The charge generation layer 3a is, for example, a single layer. Although the thickness of the charge generation layer 3a is not particularly limited, it is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 3 μm or less.

The charge transport layer 3b is, for example, a single layer. Although the thickness of the charge transport layer 3b is not particularly limited, it is preferably 2 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.

As shown in FIGS. 1 and 3, it is preferable that the charge transport layer 3b is a single layer and provided as the outermost layer of the photoreceptor 1. FIG. The charge transport layer 3b containing the polyarylate resin (PA) described later and the azo compound represented by the general formula (30) described later in the same layer is provided as the outermost layer, thereby improving the abrasion resistance of the photoreceptor 1. is further improved. In addition, as shown in FIG. 2, the charge generation layer 3a may be provided as the outermost surface layer of the photoreceptor 1. FIG. A protective layer may also be provided as the outermost surface layer of the photoreceptor 1 . The structure of the photoreceptor 1 has been described above with reference to FIGS. 1 to 3. FIG. The photoreceptor will be described in more detail below.

[Charge generation layer]
The charge generation layer contains a charge generation agent. The charge generation layer may further contain a base resin, if desired. The charge generation layer may further contain additives, if desired.

(Charge generating agent)
Examples of charge generating agents include phthalocyanine pigments, perylene pigments, bisazo pigments, trisazo pigments, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaline pigments, indigo pigments, azulenium pigments, cyanine pigments, Pigments, powders of inorganic photoconductive materials (e.g. selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, and amorphous silicon), pyrylium pigments, anthanthrone-based pigments, triphenylmethane-based pigments, threne-based pigments, toluidine-based pigments , pyrazoline-based pigments, and quinacridone-based pigments. The charge-generating layer may contain only one charge-generating agent, or may contain two or more charge-generating agents.

A phthalocyanine pigment is a pigment having a phthalocyanine structure. Examples of phthalocyanine pigments include metal-free phthalocyanines and metal phthalocyanines. Metal phthalocyanines include, for example, titanyl phthalocyanine, hydroxygallium phthalocyanine, and chlorogallium phthalocyanine. A metal-free phthalocyanine is represented by the chemical formula (CGM-1). Titanyl phthalocyanine is represented by the chemical formula (CGM-2).

The phthalocyanine pigment may be crystalline or amorphous. Examples of metal-free phthalocyanine crystals include X-type crystals of metal-free phthalocyanine (hereinafter sometimes referred to as X-type metal-free phthalocyanine). Examples of titanyl phthalocyanine crystals include α-type, β-type, and Y-type crystals of titanyl phthalocyanine (hereinafter sometimes referred to as α-type, β-type, and Y-type titanyl phthalocyanine).

For example, it is preferable to use a photoreceptor having sensitivity in a wavelength region of 700 nm or more for a digital optical image forming apparatus (for example, a laser beam printer or facsimile using a light source such as a semiconductor laser). As the charge generating agent, a phthalocyanine-based pigment is preferred, metal-free phthalocyanine or titanyl phthalocyanine is more preferred, titanyl phthalocyanine is still more preferred, and Y-type titanyl phthalocyanine is particularly preferred, since it has a high quantum yield in a wavelength region of 700 nm or more. .

Y-type titanyl phthalocyanine has a main peak at, for example, a Bragg angle (2θ±0.2°) of 27.2° in its CuKα characteristic X-ray diffraction spectrum. The main peak in the CuKα characteristic X-ray diffraction spectrum is the peak having the first or second highest intensity in the range where the Bragg angle (2θ±0.2°) is 3° or more and 40° or less. Y-type titanyl phthalocyanine does not have a peak at 26.2° C. in its CuKα characteristic X-ray diffraction spectrum.

The CuKα characteristic X-ray diffraction spectrum can be measured, for example, by the following method. First, a sample (titanyl phthalocyanine) is filled in a sample holder of an X-ray diffraction device (for example, "RINT (registered trademark) 1100" manufactured by Rigaku Corporation), and the X-ray tube Cu, tube voltage 40 kV, tube current 30 mA, Also, the X-ray diffraction spectrum is measured under the condition that the wavelength of the CuKα characteristic X-ray is 1.542 Å. The measurement range (2θ) is, for example, 3° or more and 40° or less (start angle: 3°, stop angle: 40°), and the scanning speed is, for example, 10°/min. A main peak is determined from the obtained X-ray diffraction spectrum, and the Bragg angle of the main peak is read.

The content of the charge generating agent is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 100 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the base resin.

(base resin)
Examples of base resins include thermoplastic resins (more specifically, polycarbonate resins, styrene resins, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, styrene-acrylic acid Copolymers, acrylic copolymers, polyethylene resins, ethylene-vinyl acetate copolymers, chlorinated polyethylene resins, polyvinyl chloride resins, polypropylene resins, ionomers, vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd resins, polyamide resins, polyurethane resins, polysulfone resins, diallyl phthalate resins, ketone resins, polyvinyl butyral resins, polyvinyl acetal resins, and polyether resins), thermosetting resins (more specifically, silicone resins, epoxy resins, phenol resins, urea resins, melamine resins, and other crosslinkable thermosetting resins), and photocurable resins (more specifically, epoxy-acrylic acid-based resins and urethane-acrylic acid-based copolymers). .

(Additive)
Additives contained in the charge generation layer include, for example, ultraviolet absorbers, antioxidants, radical scavengers, singlet quenchers, softeners, surface modifiers, extenders, thickeners, and dispersion stabilizers. , waxes, donors, surfactants, plasticizers, sensitizers, and leveling agents.

[Charge transport layer]
The charge transport layer contains a binder resin, an azo compound and a hole transport agent. The charge transport layer preferably further contains an electron acceptor compound. The charge transport layer may further contain additives, if desired.

(binder resin)
The binder resin comprises a polyarylate resin having at least one first repeating unit, at least one second repeating unit, and terminal groups. The first repeating unit is represented by general formula (1). The second repeating unit is represented by general formula (2). A terminal group is represented by General formula (3). Hereinafter, at least one first repeating unit represented by the general formula (1), at least one second repeating unit represented by the general formula (2), and a terminal represented by the general formula (3) A polyarylate resin having a group is sometimes described as a "polyarylate resin (PA)". The first repeating unit represented by formula (1) may be described as "repeating unit (1)". The second repeating unit represented by formula (2) may be described as "repeating unit (2)". The terminal group represented by general formula (3) may be described as "terminal group (3)".

In general formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ may combine with each other to represent a divalent group represented by general formula (X). In general formula (2), X ¹ represents a divalent group represented by chemical formula (2A), (2B), (2C), or (2D). In general formula (3), R ^f represents a chain aliphatic group having 1 or more and 20 or less carbon atoms substituted with one or more fluorine atoms.

In general formula (X), t represents an integer of 1 or more and 3 or less. * represents a bond. Specifically, * represents a bond to the carbon atom to which X ¹ in general formula (2) is bonded.

A polyarylate resin (PA) has a repeating unit with a specific structure, and is therefore excellent in strength. Since the terminal group (3) of the polyarylate resin (PA) has a fluorine atom and the main chain does not have a halogen atom, the main chains are easily entangled with each other and the strength is excellent. Since the polyarylate resin (PA) has terminal groups containing chain aliphatic groups substituted with fluorine atoms, the frictional resistance on the surface of the charge transport layer is reduced. For these reasons, the abrasion resistance of the photoreceptor is improved by including the polyarylate resin (PA) in the charge transport layer.

Furthermore, the polyarylate resin (PA) has a fluorine atom in the terminal group (3) and does not have a halogen atom in the main chain. Crystallization of the layer can be suppressed.

Polyarylate resin (PA) has a backbone and end groups (3). The main chain and terminal groups (3) of the polyarylate resin (PA) are described below.

The backbone of the polyarylate resin (PA) comprises at least one repeating unit (1) and at least one repeating unit (2).

The repeating unit (1) will be described below. The alkyl group having 1 to 4 carbon atoms represented by R ⁵ and R ⁶ in general formula (1) is preferably a methyl group or an ethyl group.

t in the general formula (X) is preferably 1 or 2, more preferably 2.

When R ⁵ and R ⁶ in general formula (1) are bonded to each other to represent a divalent group represented by general formula (X), R ¹ and R ³ each represent a methyl group, and R ² and Each R ⁴ preferably represents a hydrogen atom.

At least one repeating unit (1) is at least one repeating unit represented by chemical formulas (1-1), (1-2), (1-3), and (1-4) Units are preferred. Hereinafter, repeating units represented by chemical formulas (1-1), (1-2), (1-3), and (1-4) are respectively replaced by repeating units (1-1) and (1-2) , (1-3), and (1-4).

The polyarylate resin (PA) may contain only one repeating unit (1), or may contain two or more (for example, two) repeating units (1).

When the polyarylate resin (PA) contains two types of repeating units (1), the ratio of the number of one repeating unit (1) to the total number of the two types of repeating units (1) (hereinafter referred to as the ratio r ) is preferably 0.10 or more and 0.90 or less.

Next, repeating unit (2) will be described. As the repeating unit (2), repeating units represented by general formulas (2-1) and (2-2) (hereinafter referred to as repeating units (2-1) and (2-2), respectively) there is) is preferred. In general formula (2-2) below, X ² represents a divalent group represented by chemical formula (2A), (2B) or (2D).

At least one repeating unit (2) is at least one repeating unit represented by chemical formulas (2-1C), (2-2A), (2-2B), and (2-2D) Units are preferred. Hereinafter, repeating units represented by chemical formulas (2-1C), (2-2A), (2-2B), and (2-2D) are respectively replaced by repeating units (2-1C) and (2-2A). , (2-2B), and (2-2D).

The polyarylate resin (PA) may contain only one repeating unit (2), or may contain two or more (for example, two) repeating units (2). When the polyarylate resin (PA) contains one type of repeating unit (2), the repeating unit (2) may be a repeating unit (2-2A), (2-2B), or (2-2D). Preferably, the repeating unit (2-2A) is more preferable.

From the viewpoint of further improving the wear resistance of the photoreceptor, the polyarylate resin (PA) preferably has two or more types of repeating units (2). ) and more preferably. From the same point of view, it is particularly preferable that the polyarylate resin (PA) has, as repeating units (2), one type of repeating unit (2-1) and one type of repeating unit (2-2).

When the polyarylate resin (PA) contains two types of repeating units (2), the two types of repeating units (2) are preferably repeating units (2-1C) and repeating units (2-2A). It is also preferred that the two repeating units (2) are the repeating unit (2-1C) and the repeating unit (2-2B). It is also preferred that the two types of repeating units (2) are repeating units (2-1C) and repeating units (2-2D).

From the viewpoint of further improving the abrasion resistance of the photoreceptor, the ratio of the number of repeating units (2-1) to the total number of repeating units (2) (hereinafter sometimes referred to as ratio p) is 0.05. 0.10 to 0.70, still more preferably 0.30 to 0.70, still more preferably 0.50 to 0.70, and 0.60 to 0.60. 70 or less is particularly preferred.

Note that the ratio p and the already-described ratio r are not values obtained from one molecular chain, but from the entire polyarylate resin (PA) contained in the charge transport layer (a plurality of molecular chains). It is the mean value of the values obtained. The proportion of each repeating unit can be calculated from the ¹ H-NMR spectrum obtained by measuring the ¹ H-NMR spectrum of the polyarylate resin (PA) using a proton nuclear magnetic resonance spectrometer.

Next, the terminal group (3) will be explained. The fluorine atom-substituted chain aliphatic group represented by R ^f in the general formula (3) is linear or branched. The number of fluorine atoms substituting the chain aliphatic group is preferably 1 or more and 37 or less, more preferably 1 or more and 17 or less. In addition, the terminal group (3) is acyclic. Since the terminal group (3) is not a cyclic group but a chain aliphatic group, the wear resistance of the photoreceptor can be improved. Here, the "chain aliphatic group" is, for example, a monovalent chain hydrocarbon group (especially an alkyl group), or a group in which -O- is inserted between the carbon-carbon bonds of a chain hydrocarbon group. be.

As the terminal group (3), a terminal group represented by the following general formula (3-1) (hereinafter sometimes referred to as a terminal group (3-1)) is preferable. By having the terminal group (3-1) in the polyarylate resin (PA), the friction resistance on the surface of the charge transport layer can be further reduced, and the wear resistance of the photoreceptor can be further improved.

In general formula (3-1), R ³¹ represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. R ³² represents a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. n represents an integer of 0 or more and 2 or less. When n represents 2, two R ³² may represent the same group or different groups.

The perfluoroalkyl group represented by R ³¹ in general formula (3-1) is preferably a linear or branched perfluoroalkyl group having 3 or more and 6 or less carbon atoms. A perfluoroalkyl group having a number of 3 or more and 6 or less is more preferable, and a heptafluoro n-propyl group or tridecafluoro n-hexyl group is even more preferable.

The perfluoroalkylene group represented by R ³² in the general formula (3-1) is preferably a linear or branched perfluoroalkylene group having 2 or 3 carbon atoms, such as 1-fluoro-1-tri A fluoromethyl-methylene group or a 1,1,2-trifluoro-2-trifluoromethyl-ethylene group is more preferred.

From the viewpoint of further improving the abrasion resistance of the photoreceptor, preferred examples of the terminal group (3) include terminal groups represented by chemical formulas (M1), (M2), (M3), and (M4) (hereinafter , which are sometimes referred to as terminal groups (M1), (M2), (M3), and (M4), respectively).

Terminal group (M1), (M3), or (M4) is more preferable as the terminal group (3) from the viewpoint of further improving the abrasion resistance of the photoreceptor. In addition, the longer the carbon chain of the terminal group (3) and the more fluorine atoms it has, the lower the friction resistance on the surface of the charge transport layer tends to be. For these reasons, the terminal group (3) is more preferably the terminal group (M1) or (M3), and particularly preferably the terminal group (M3).

As the polyarylate resin (PA), polyarylate resins (j-1) to (j-11) shown in Table 1 below are preferred.

The terms used in Table 1 and Tables 2 and 6, which will be described later, have the following meanings. "Unit (1)" and "Unit (2)" represent repeating units (1) and (2), respectively. When two repeating units are described in repeating unit (1) or repeating unit (2), it indicates that both of them are included. For example, "1-2/1-3" in Table 1 indicates having both repeating units (1-2) and (1-3). "-" indicates that there is no applicable value.

As the polyarylate resin (PA), more polyarylate resins (R-1-M1) to (R-10-M1) and (R-1-M2) to (R-1-M4) shown in Table 2 below are used. preferable.

In the polyarylate resin (PA), the repeating unit derived from the aromatic diol and the repeating unit derived from the aromatic dicarboxylic acid are adjacently bonded to each other. A repeating unit derived from an aromatic diol is, for example, repeating unit (1). A repeating unit derived from an aromatic dicarboxylic acid is, for example, repeating unit (2). In addition, in the polyarylate resin (PA), the terminal group (3) is adjacent to and bound to the repeating unit derived from the aromatic dicarboxylic acid. When the polyarylate resin (PA) is a copolymer, the polyarylate resin (PA) may be, for example, a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. .

The polyarylate resin (PA) preferably has only repeating units (1) and (2) as repeating units. However, the polyarylate resin (PA) may further have a repeating unit derived from an aromatic diol other than the repeating unit (1), and may further have a repeating unit derived from an aromatic dicarboxylic acid other than the repeating unit (2). You may

The viscosity average molecular weight of the polyarylate resin (PA) is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and particularly preferably 40,000 or more. When the viscosity average molecular weight of the polyarylate resin (PA) is 10,000 or more, the abrasion resistance of the binder resin can be further improved. On the other hand, the viscosity average molecular weight of the binder resin is preferably 80,000 or less, more preferably 70,000 or less. When the viscosity-average molecular weight of the binder resin is 80,000 or less, the polyarylate resin (PA) is easily dissolved in the solvent for forming the charge transport layer, so that the charge transport layer can be preferably formed.

The method for producing the polyarylate resin (PA) is not particularly limited. A method of polycondensing is mentioned. As the condensation polymerization method, a known synthesis method (more specifically, solution polymerization, melt polymerization, interfacial polymerization, or the like) can be adopted.

An aromatic diol for constituting the main chain is represented, for example, by general formula (BP-1) below. An aromatic dicarboxylic acid for constituting the main chain is represented by, for example, general formula (DC-2) below. The terminal terminator for forming the terminal group (3) is represented, for example, by general formula (T-3) below. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X ¹ and R ^f in the following general formulas (BP-1), (DC-2) and (T-3) are each general It has the same meaning as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X ¹ and R ^f in formulas (1), (2) and (3). Hereinafter, the compounds represented by the following general formulas (BP-1), (DC-2), and (T-3) are respectively converted to compounds (BP-1), (DC-2), and (T-3). ) may be described.

As the compound (BP-1), compounds represented by the chemical formulas (BP-1-1) to (BP-1-4) (hereinafter referred to as compounds (BP-1-1) to (BP-1-4 ) is preferred.

As the compound (DC-2), compounds represented by the following chemical formulas (DC-2-1C), (DC-2-2A), (DC-2-2B), and (DC-2-2D) (hereinafter , which are sometimes referred to as compounds (DC-2-1C), (DC-2-2A), (DC-2-2B), and (DC-2-2D)).

As the compound (T-3), compounds represented by the following chemical formulas (T-M1) to (T-M4) (hereinafter each may be described as compounds (T-M1) to (T-M4) ) is preferred.

In addition, the aromatic diol for constituting the main chain may be used after being modified into an aromatic diacetate. Aromatic dicarboxylic acids for constituting the main chain may be used after being derivatized. Derivatives of aromatic dicarboxylic acids include, for example, aromatic dicarboxylic acid dichloride, aromatic dicarboxylic acid dimethyl ester, aromatic dicarboxylic acid diethyl ester, and aromatic dicarboxylic acid anhydride. An aromatic dicarboxylic acid dichloride is a compound in which two "-C(=O)-OH" groups of an aromatic dicarboxylic acid are each substituted with a "-C(=O)-Cl" group.

One or both of a base and a catalyst may be added in the polycondensation of an aromatic diol and an aromatic dicarboxylic acid. The base and catalyst can be appropriately selected from known bases and catalysts. Bases include, for example, sodium hydroxide. Catalysts include, for example, benzyltributylammonium chloride, ammonium chloride, ammonium bromide, quaternary ammonium salts, triethylamine, and trimethylamine.

The charge transport layer preferably contains only polyarylate resin (PA) as a binder resin. The charge transport layer may further contain, as a binder resin, a binder resin other than the polyarylate resin (PA) (hereinafter sometimes referred to as other binder resin). Examples of other binder resins are the same as those of the base resin.

(azo compound)
Azo compounds are represented by general formula (30). Hereinafter, the azo compound represented by general formula (30) may be referred to as azo compound (30).

In general formula (30), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 3 carbon atoms. Ar ¹ and Ar ² each independently represent an arylene group having 6 to 14 carbon atoms which may be substituted with at least one substituent. The substituent substituting the arylene group having 6 to 14 carbon atoms is selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and alkoxy groups having 1 to 3 carbon atoms. Q represents a monovalent group represented by general formula (Q1) or (Q2).

In general formula (Q1), Ar ³ and Ar ⁴ each independently represent an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms. * represents a bond. In general formula (Q2), Z represents a 6- to 18-membered heterocyclic ring having at least a nitrogen atom as a ring-constituting atom. * represents a bond.

By containing the azo compound (30) in the charge transport layer, the light resistance of the photoreceptor to white light is improved. Specifically, during maintenance of the image forming apparatus, the photoreceptor provided in the image forming apparatus may be exposed to white light (for example, white light from a fluorescent lamp). When an image is formed using an imaging apparatus after exposure to white light, the post-exposure potential of the peripheral surface area of the photoreceptor exposed to white light may drop below the desired post-exposure potential. Hereinafter, the area of the peripheral surface of the photoreceptor exposed to white light will be referred to as "light-exposed area". Also, the area of the peripheral surface of the photoreceptor that has not been exposed to white light is referred to as a "non-light-exposed area." In the formed image, the image density of the image areas corresponding to the light-exposed areas whose post-exposure potential is lower than the desired post-exposure potential is higher than the image density of the image areas corresponding to the non-light-exposed areas. Here, the azo compound (30) absorbs white light exposed to the photoreceptor. Therefore, the photoreceptor having the charge-transporting layer containing the azo compound (30) can prevent the post-exposure potential of the light-exposed region from lowering below the desired value, resulting from exposure to white light. It is possible to suppress the occurrence of image defects caused by Thus, the photoreceptor of this embodiment has excellent light resistance to white light.

Further, by containing the azo compound (30) in addition to the polyarylate resin (PA) in the charge transport layer, the wear resistance of the photoreceptor improved by the polyarylate resin (PA) is further improved.

The general formula (30) will be further described below. The alkyl group having 1 to 3 carbon atoms represented by R ¹¹ and R ¹² is preferably a methyl group or an ethyl group.

The arylene group having 6 to 14 carbon atoms represented by Ar ¹ and Ar ² is preferably an arylene group having 6 to 10 carbon atoms, more preferably a phenylene group, and still more preferably a p-phenylene group. The arylene group having 6 to 14 carbon atoms represented by Ar ¹ and Ar ² may be substituted with at least one substituent. Such substituents are preferably one or two substituents selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and alkoxy groups having 1 to 3 carbon atoms. Such substituents are more preferably one or two substituents selected from the group consisting of methyl, ethyl and methoxy groups. The arylene group having 6 to 14 carbon atoms which may be substituted with at least one substituent represented by Ar ¹ and Ar ² includes a phenylene group, a methylphenylene group, an ethylphenylene group, a dimethylphenylene group, or a methoxyphenylene group. is preferred. The arylene groups having 6 to 14 carbon atoms which may be substituted with at least one substituent represented by Ar ¹ and Ar ² include p-phenylene group, 2-methyl-1,4-phenylene group, 3- methyl-1,4-phenylene group, 2-ethyl-1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 2,6-dimethyl-1,4-phenylene group, or 3-methoxy A -1,4-phenylene group is more preferred.

As already mentioned, * in general formulas (Q1) and (Q2) represents a bond. Specifically, * represents a bond to the nitrogen atom to which Q is bonded in general formula (30).

The aryl group having 6 to 14 carbon atoms represented by Ar ³ and Ar ⁴ in general formula (Q1) is preferably a phenyl group or a naphthyl group. As the naphthyl group, a 1-naphthyl group is preferred. The aryl group having 6 to 14 carbon atoms represented by Ar ³ and Ar ⁴ may be substituted with an alkyl group having 1 to 3 carbon atoms.

As already described, Z in general formula (Q2) represents a 6- to 18-membered heterocyclic ring having at least a nitrogen atom as a ring-constituting atom. N in general formula (Q2) represents a nitrogen atom that is a ring-constituting atom. A nitrogen atom, which is a ring-constituting atom shown in general formula (Q2), has a bond. Specifically, the nitrogen atom, which is a ring-constituting atom shown in general formula (Q2), is bonded to the nitrogen atom to which Q in general formula (30) is bonded.

As the 6- to 18-membered heterocyclic ring represented by Z in the general formula (Q2), a 13- to 15-membered heterocyclic ring is preferable. The monovalent group represented by general formula (Q2) is preferably a monovalent group represented by general formula (Q2-1) or chemical formula (Q2-2) below.

In general formula (Q2-1), W represents -CH ₂ - or -O-. p represents an integer of 0 or more and 2 or less. When p represents 2, two W may represent the same group or different groups. In general formula (Q2-1) and chemical formula (Q2-2), * represents a bond. In general formula (Q2-1), it is preferred that W represents an oxygen atom and p represents 1. It is also preferred that p represents 0 in general formula (Q2-1).

Examples of the azo compound (30) include the compounds represented by the chemical formulas (ADD-1) to (ADD-8) (hereinafter referred to as azo compounds (ADD-1) to (ADD-8), respectively. There is).

The content of the azo compound (30) is 2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin. If the content of the azo compound (30) is less than 2 parts by mass with respect to 100 parts by mass of the binder resin, the light resistance to white light is lowered. On the other hand, if the content of the azo compound (30) is more than 5 parts by mass with respect to 100 parts by mass of the binder resin, the wear resistance of the photoreceptor is lowered. In order to achieve a well-balanced improvement in wear resistance of the photoreceptor and improvement in light resistance to white light, the content of the azo compound (30) is 3 parts by mass or more with respect to 100 parts by mass of the binder resin. It is preferably 5 parts by mass or less, and more preferably 3 parts by mass or more and 4 parts by mass or less.

(Hole transport agent)
Examples of hole transport agents include triphenylamine derivatives, diamine derivatives (e.g., N,N,N',N'-tetraphenylbenzidine derivatives, N,N,N',N'-tetraphenylphenylenediamine derivatives, N,N,N',N'-tetraphenylnaphthylenediamine derivatives, N,N,N',N'-tetraphenylphenanthrylenediamine derivatives, and di(aminophenylethenyl)benzene derivatives), oxadiazole compounds (e.g., 2,5-di(4-methylaminophenyl)-1,3,4-oxadiazole), styryl compounds (e.g., 9-(4-diethylaminostyryl)anthracene), carbazole compounds ( polyvinylcarbazole), organic polysilane compounds, pyrazoline compounds (e.g., 1-phenyl-3-(p-dimethylaminophenyl)pyrazoline), hydrazone compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole thiadiazole-based compounds, imidazole-based compounds, pyrazole-based compounds, and triazole-based compounds. The charge transport layer may contain only one hole transport agent, or may contain two or more hole transport agents.

The hole transport agent preferably contains a compound represented by the following general formula (10) (hereinafter sometimes referred to as hole transport agent (10)). By containing the hole transport agent (10) in the charge transport layer, abrasion resistance, light resistance to white light, charging characteristics, and sensitivity characteristics of the photoreceptor can be further improved.

In general formula (10), R ¹⁰¹ , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a carbon atom represents a phenyl group optionally substituted with an alkyl group having 1 or more and 8 or less, or an alkoxy group having 1 or more and 8 or less carbon atoms; Adjacent two of R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ may combine to represent a cycloalkane having 5 or more and 7 or less carbon atoms. R ¹⁰² and R ¹⁰⁹ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms. b ₁ and b ₂ each independently represent an integer of 0 or more and 5 or less.

In general formula (10), the alkyl group having 1 to 8 carbon atoms represented by R ¹⁰¹ to R ¹⁰⁹ is preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. is more preferred, and an n-butyl group is even more preferred.

In general formula (10), the phenyl group represented by R ¹⁰¹ to R ¹⁰⁹ may be substituted with an alkyl group having 1 to 8 carbon atoms. As such an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is still more preferable.

In general formula (10), the alkoxy group having 1 to 8 carbon atoms represented by R ¹⁰¹ to R ¹⁰⁹ is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.

In general formula (10), adjacent two of R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ may combine with each other to represent a cycloalkane having 5 or more and 7 or less carbon atoms. When adjacent two of R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ are combined to form a cycloalkane having 5 or more and 7 or less carbon atoms, the cycloalkane is R ¹⁰³ , R ¹⁰⁴ , It is condensed with the phenyl group to which R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ are attached to form a bicyclic condensed ring group. In this case, the condensation site between the cycloalkane and the phenyl group may contain a double bond. Cyclohexane is preferred as the cycloalkane in which adjacent two of R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ are bonded to each other.

When b ₁ represents an integer of 2 or more and 5 or less, a plurality of R ¹⁰² may represent the same group or different groups. When b ₂ represents an integer of 2 or more and 5 or less, a plurality of R ¹⁰⁹ may represent the same group or different groups. b ₁ and b ₂ preferably each independently represent 0 or 1;

In general formula (10), R ¹⁰¹ and R ¹⁰⁸ preferably represent hydrogen atoms. R ¹⁰² and R ¹⁰⁹ preferably represent an alkyl group having 1 to 8 carbon atoms. R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁶ and R ¹⁰⁷ each preferably represent a hydrogen atom. R ¹⁰⁵ preferably represents an alkyl group having 1 to 8 carbon atoms, more preferably an n-butyl group. b ₁ and b ₂ preferably each independently represent 0;

As the hole transport agent (10), a compound represented by the following chemical formula (HTM-1) (hereinafter sometimes referred to as hole transport agent (HTM-1)) is preferable.

The charge transport layer preferably contains only the hole transport agent (10) as a hole transport agent, but may further contain a hole transport agent other than the hole transport agent (10).

The content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Electron acceptor compound)
Examples of electron acceptor compounds include quinone compounds, diimide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride, and dibromomaleic anhydride. Examples of quinone compounds include diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds, and dinitroanthraquinone compounds.

As the electron acceptor compound, a compound represented by the following general formula (20) (hereinafter sometimes referred to as an electron acceptor compound (20)) is preferable. By containing the electron acceptor compound (20) in the charge transport layer, abrasion resistance, light resistance to white light, charging characteristics, and sensitivity characteristics of the photoreceptor can be further improved.

In general formula (20), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 6 carbon atoms. R ²¹ , R ²² , R ²³ and R ²⁴ preferably each independently represent an alkyl group having 3 or more and 5 or less carbon atoms.

As the compound represented by the general formula (20), a compound represented by the following chemical formula (E-1) (hereinafter sometimes referred to as an electron acceptor compound (E-1)) is preferable.

The content of the electron acceptor compound is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin.

The charge transport layer may contain only one electron acceptor compound, or may contain two or more electron acceptor compounds. The charge transport layer may contain only the electron acceptor compound (20) as the electron acceptor compound, or may further contain an electron acceptor compound other than the electron acceptor compound (20).

(Additive)
The charge transport layer may contain only the hole transport agent, binder resin, electron acceptor compound, and azo compound (30), or may further contain additives other than these. Examples of additives contained in the charge transport layer are the same as those already described for the charge generation layer. In order for the exposure light to reach the charge generation layer appropriately, the charge transport layer preferably does not contain a phthalocyanine pigment, and more preferably does not contain either or both of titanyl phthalocyanine and metal-free phthalocyanine.

(combination of materials)
In order to improve abrasion resistance and white light resistance, combinations of polyarylate resins and azo compounds are selected from combination Nos. shown in Tables 3 to 5. Each of 1 to 192 is preferred. In Tables 3 to 5, "No." indicates combination No. , "resin" indicates a polyarylate resin, and "azo" indicates an azo compound.

In order to improve abrasion resistance and white light resistance, a combination of a polyarylate resin and an azo compound is used as combination No. 1 above. 1 to 192, and the hole transport agent is preferably a hole transport agent (HTM-1). For the same reason, the combination of polyarylate resin and azo compound is combination No. 1 to 192, and the electron acceptor compound is preferably the electron acceptor compound (E-1). For the same reason, the combination of polyarylate resin and azo compound is combination No. 1 to 192, the hole transport agent is the hole transport agent (HTM-1), and the electron acceptor compound is preferably the electron acceptor compound (E-1).

In order to improve abrasion resistance and white light resistance, a combination of a polyarylate resin and an azo compound is used as combination No. 1 above. 1 to 192, the hole transport agent is a hole transport agent (HTM-1), and the charge generating agent is preferably Y-type titanyl phthalocyanine. For the same reason, the combination of polyarylate resin and azo compound is combination No. 1 to 192, the electron acceptor compound is the electron acceptor compound (E-1), and the charge generating agent is preferably Y-type titanyl phthalocyanine. For the same reason, the combination of polyarylate resin and azo compound is combination No. 1 to 192, the hole transport agent is the hole transport agent (HTM-1), the electron acceptor compound is the electron acceptor compound (E-1), and the charge generator is Y-type titanyl phthalocyanine. is preferred.

[Conductive substrate]
The conductive substrate is not particularly limited as long as it can be used as the conductive substrate of the photoreceptor. At least the surface portion of the conductive substrate may be made of a conductive material. An example of the conductive substrate is a conductive substrate made of a conductive material. Another example of a conductive substrate is a conductive substrate coated with a material having electrical conductivity. Conductive materials include, for example, aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass. These conductive materials may be used alone, or two or more of them may be used in combination (for example, as an alloy). Among these materials having conductivity, aluminum and aluminum alloys are preferable because charge transfer from the charge generation layer to the conductive substrate is favorable.

The shape of the conductive substrate is appropriately selected according to the structure of the image forming apparatus. Examples of the shape of the conductive substrate include a sheet shape and a drum shape. Moreover, the thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.

[Middle layer]
The intermediate layer (undercoat layer) contains, for example, inorganic particles and a resin used for the intermediate layer (intermediate layer resin). The presence of the intermediate layer makes it possible to maintain an insulating state to the extent that leakage can be suppressed, and to smooth the flow of current generated when the photosensitive member is exposed to light, thereby suppressing an increase in resistance.

Examples of inorganic particles include particles of metals (e.g., aluminum, iron, and copper), particles of metal oxides (e.g., titanium oxide, alumina, zirconium oxide, tin oxide, and zinc oxide), and non-metal oxides. (eg, silica) particles. One of these inorganic particles may be used alone, or two or more thereof may be used in combination.

Examples of the intermediate layer resin are the same as the examples of other binder resins already described. In order to form the intermediate layer and the photosensitive layer satisfactorily, the resin for the intermediate layer is preferably different from the binder resin and the base resin contained in the photosensitive layer. The intermediate layer may contain additives. Examples of additives contained in the intermediate layer are the same as the examples of other additives already described.

[Manufacturing method of photoreceptor]
Next, an example of a method for manufacturing a photoreceptor will be described. A photoreceptor manufacturing method includes a charge generating layer forming step and a charge transport layer forming step.

In the charge generation layer forming step, a coating liquid for forming the charge generation layer (hereinafter sometimes referred to as a charge generation layer forming coating liquid) is prepared. A coating liquid for forming a charge generation layer is applied onto a conductive substrate. Next, at least part of the solvent contained in the coated coating solution for forming the charge generation layer is removed to form the charge generation layer. The charge-generating layer-forming coating liquid contains, for example, a charge-generating agent, a base resin, and a solvent. Such a coating liquid for forming a charge generation layer is prepared by dissolving or dispersing a charge generation agent and a base resin in a solvent. The coating liquid for forming the charge generation layer may contain other additives, if necessary.

In the charge transport layer forming step, a coating liquid for forming the charge transport layer (hereinafter sometimes referred to as a charge transport layer forming coating liquid) is prepared. A coating liquid for forming a charge transport layer is applied onto the charge generation layer. Next, at least part of the solvent contained in the coated coating liquid for forming the charge transport layer is removed to form the charge transport layer. The charge transport layer forming coating liquid contains a hole transport agent, a binder resin, an azo compound (30), and a solvent. The coating liquid for forming the charge transport layer can be prepared by dissolving or dispersing the hole transporting agent, the binder resin and the azo compound (30) in a solvent. The coating liquid for forming the charge transport layer may further contain an electron acceptor compound and an additive, if necessary.

The solvent contained in the charge-generating layer-forming coating liquid and the charge-transporting layer-forming coating liquid (hereinafter sometimes collectively referred to as coating liquid) is not particularly limited. Examples of solvents include alcohols (more specifically, methanol, ethanol, isopropanol, butanol, etc.), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, etc.), aromatic hydrocarbons, etc. Hydrogen (more specifically, benzene, toluene, xylene, etc.), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.), ethers (more specifically, dimethyl ether , diethyl ether, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (more specifically, ethyl acetate, and methyl acetate, etc.), dimethylformaldehyde, dimethylformamide, and dimethylsulfoxide. These solvents may be used alone or in combination of two or more.

The solvent contained in the charge-transporting layer-forming coating liquid is preferably different from the solvent contained in the charge-generating layer-forming coating liquid. Also, the binder resin contained in the charge transport layer is preferably different from the base resin contained in the charge generation layer. This is because when the charge-transporting layer-forming coating liquid is applied onto the charge-generating layer, it is preferable that the charge-generating layer does not dissolve in the solvent of the charge-transporting layer-forming coating liquid.

The coating liquid is prepared by mixing each component and dispersing it in a solvent. For mixing or dispersing, for example, a bead mill, roll mill, ball mill, attritor, paint shaker, or ultrasonic disperser can be used.

In order to improve the dispersibility of each component or the surface smoothness of each layer to be formed, the coating liquid may contain, for example, a surfactant or a leveling agent.

The method of applying the coating liquid is not particularly limited as long as it is a method capable of uniformly applying the coating liquid. Examples of coating methods include dip coating, spray coating, spin coating, and bar coating.

The method for removing at least part of the solvent contained in the coating liquid is not particularly limited as long as it is a method capable of evaporating the solvent in the coating liquid. Methods of removal include, for example, heating, reduced pressure, and combined use of heating and reduced pressure. More specifically, a method of heat-treating (hot-air drying) using a high-temperature dryer or a reduced-pressure dryer is exemplified. The heat treatment temperature is, for example, 40° C. or higher and 150° C. or lower. The heat treatment time is, for example, 3 minutes or more and 120 minutes or less.

Incidentally, the method for manufacturing a photoreceptor may further include a step of forming an intermediate layer, if necessary. A known method can be appropriately selected for the step of forming the intermediate layer.

EXAMPLES Hereinafter, the present invention will be described more specifically using examples. However, the present invention is in no way limited to the scope of the examples.

(Charge generating agent, hole transport agent, and electron acceptor compound)
As a charge generating agent to be contained in the charge generating layer, the Y-type titanyl phthalocyanine described in the embodiment was prepared. As a hole transport agent to be contained in the charge transport layer, the hole transport agent (HTM-1) described in the embodiment was prepared. As an electron acceptor compound to be contained in the charge transport layer, the electron acceptor compound (E-1) described in the embodiment was prepared.

(azo compound (30))
As the azo compound (30), the azo compounds (ADD-1) to (ADD-8) described in the embodiment were prepared.

(Other compounds used in Comparative Examples)
As other compounds used in Comparative Examples, compounds represented by the following chemical formulas (ADD-E1) to (ADD-E11) (each of which is hereinafter referred to as other compound (ADD-E1) to (ADD-E11) may be done) was prepared. None of the other compounds (ADD-E1) to (ADD-E11) were included in the general formula (30) and were used in place of the azo compound (30) in Comparative Examples. The electron acceptor compound (E-1) and the other compound (ADD-E1) are the same compound, but for convenience of explanation, when used as an electron acceptor compound, the term "electron acceptor compound (E-1) ”, and when it is used as another compound, it is described as “another compound (ADD-E1)”.

(binder resin)
As binder resins, polyarylate resins (R-1-M1) to (R-1-M4), (R-2-M1) to (R-10-M1), (R-1-MA), (R- 3-MA), and (R-6-MA) were synthesized. Among the polyarylate resins, polyarylate resins (R-1-M1) to (R-1-M4) and (R-2-M1) to (R-10-M1) are the polyarylates described in the embodiments. It is a polyarylate resin included in the resin (PA). repeating unit (1) and repeating unit (2) possessed by each of polyarylate resins (R-1-M1) to (R-1-M4) and (R-2-M1) to (R-10-M1); and end groups and the ratio p are shown in Table 2 above. Further, the repeating unit (1), repeating unit (2), and and end groups and the ratio p are shown in Table 6 below. "MA" of the terminal group in Table 6 indicates a group represented by the following chemical formula (MA). The yield of each polyarylate resin in the following description is a molar ratio conversion value.

(Synthesis of polyarylate resin (R-1-M1))
In the synthesis of the polyarylate resin (R-1-M1), a 2-liter three-necked flask equipped with a thermometer and a three-way cock was used as a reaction vessel. In a reaction vessel, 20.01 g (82.56 mmol) of compound (BP-1-1), 0.281 g (0.826 mmol) of compound (T-M1), 7.84 g (196 mmol) of sodium hydroxide, and 0.240 g (0.768 mmol) of benzyltributylammonium chloride was charged. The air in the reaction vessel was replaced with argon gas. An additional 600 mL of water was added to the contents of the reaction vessel. The contents of the reaction vessel were stirred at 20° C. for 1 hour. Next, the contents of the reaction vessel were cooled until the temperature of the contents of the reaction vessel reached 10° C., and an alkaline aqueous solution A was obtained.

On the other hand, 2,6-naphthalene dicarboxylic acid dichloride (dichloride of compound (DC-2-1C)) 9.84 g (38.9 mmol), and 4,4'-oxybisbenzoic acid dichloride (compound (DC-2-2A) ) was dissolved in 300 g of chloroform. A chloroform solution B was thus obtained.

The chloroform solution B was added to the alkaline aqueous solution A while stirring the alkaline aqueous solution A in the reaction vessel at 10°C. This initiated the polymerization reaction. While adjusting the temperature (liquid temperature) of the contents of the reaction vessel to 13±3° C., the contents of the reaction vessel were stirred for 3 hours to allow the polymerization reaction to proceed. Then, the upper layer (aqueous layer) in the contents of the reaction vessel was removed by decanting to obtain an organic layer. Then, 500 mL of ion-exchanged water was placed in a 2-L Erlenmeyer flask. The resulting organic layer was further added to the flask. An additional 300 g of chloroform and 6 mL of acetic acid were added to the flask. The flask contents were then stirred at room temperature for 30 minutes. After that, the upper layer (aqueous layer) in the contents of the flask was removed by decanting to obtain an organic layer. Using a separating funnel, the obtained organic layer was washed with 500 mL of ion-exchanged water. Washing with ion-exchanged water was repeated eight times to obtain a water-washed organic layer.

Next, the washed organic layer was filtered to obtain a filtrate. 1.5 L of methanol was placed in a 3 L beaker. The resulting filtrate was slowly added dropwise to methanol in a beaker to obtain a precipitate. The precipitate was removed by filtration. The sediment taken out was vacuum-dried at a temperature of 70° C. for 12 hours. As a result, a polyarylate resin (R-1-M1) was obtained (yield: 28.6 g, yield: 82.9%). The viscosity average molecular weight of the polyarylate resin (R-1-M1) was 50,500.

Polyarylate resins (R-1-M2) ~ (R-1-M4), (R-2-M1) ~ (R-10-M1), (R-1-MA), (R-3-MA) , and (R-6-MA) were synthesized in the same manner as the polyarylate resin (R-1-M1) except for the following changes.

(Synthesis of polyarylate resin (R-2-M1))
In the synthesis of polyarylate resin (R-2-M1), the dichloride of compound (DC-2-2A) was changed to 38.9 mmol of dichloride of compound (DC-2-2B). The yield of the obtained polyarylate resin (R-2-M1) was 27.8 g, the yield was 82.1%, and the viscosity average molecular weight was 52,200.

(Synthesis of polyarylate resin (R-3-M1))
In the synthesis of the polyarylate resin (R-3-M1), the compound (BP-1-1) was changed to 82.56 millimoles of the compound (BP-1-2). The yield of the obtained polyarylate resin (R-3-M1) was 31.0 g, the yield was 80.1%, and the viscosity average molecular weight was 48,100.

(Synthesis of polyarylate resin (R-4-M1))
In the synthesis of polyarylate resin (R-4-M1), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-2). Further, in the synthesis of the polyarylate resin (R-4-M1), the amount of the dichloride of the compound (DC-2-1C) was changed to 23.3 mmol, and the dichloride of the compound (DC-2-2A) was used. The amount was changed to 54.5 mmol. The yield of the obtained polyarylate resin (R-4-M1) was 31.3 g, the yield was 79.6%, and the viscosity average molecular weight was 47,600.

(Synthesis of polyarylate resin (R-5-M1))
In the synthesis of polyarylate resin (R-5-M1), compound (BP-1-1) was added to 8.26 mmol of compound (BP-1-2) and 74.30 mmol of compound (BP-1-3). changed. Further, in the synthesis of the polyarylate resin (R-5-M1), the amount of the dichloride of the compound (DC-2-1C) was changed to 7.8 millimoles, and the dichloride of the compound (DC-2-2A) was used. The amount was changed to 70.0 mmol. The yield of the obtained polyarylate resin (R-5-M1) was 31.2 g, the yield was 80.0%, and the viscosity average molecular weight was 49,500. Further, the obtained polyarylate resin (R-5-M1) has two kinds of repeating units (1-2) and (1-3) as the repeating unit (1), and the molar ratio (repeating unit (1-2): Repeating unit (1-3)) was 1:9.

(Synthesis of polyarylate resin (R-6-M1))
In the synthesis of polyarylate resin (R-6-M1), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-2). Further, in the synthesis of the polyarylate resin (R-6-M1), the dichloride of the compound (DC-2-2A) was changed to 38.9 millimoles of the dichloride of the compound (DC-2-2B). The yield of the obtained polyarylate resin (R-6-M1) was 30.5 g, the yield was 76.8%, and the viscosity average molecular weight was 48,900.

(Synthesis of polyarylate resin (R-7-M1))
In the synthesis of the polyarylate resin (R-7-M1), the compound (BP-1-1) was changed to 82.56 millimoles of the compound (BP-1-2). Further, in the synthesis of the polyarylate resin (R-7-M1), the dichloride of the compound (DC-2-2A) was changed to 38.9 millimoles of the dichloride of the compound (DC-2-2D). The yield of the obtained polyarylate resin (R-7-M1) was 28.9 g, the yield was 78.6%, and the viscosity average molecular weight was 47,600.

(Synthesis of polyarylate resin (R-8-M1))
In the synthesis of polyarylate resin (R-8-M1), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-4). The yield of the obtained polyarylate resin (R-8-M1) was 27.8 g, the yield was 80.6%, and the viscosity average molecular weight was 55,100.

(Synthesis of polyarylate resin (R-9-M1))
The dichloride of compound (DC-2-1C) was not used in the synthesis of polyarylate resin (R-9-M1). In the synthesis of polyarylate resin (R-9-M1), the amount of dichloride used in compound (DC-2-2A) was changed to 77.8 millimoles. The yield of the obtained polyarylate resin (R-9-M1) was 28.8 g, the yield was 79.7%, and the viscosity average molecular weight was 60,000.

(Synthesis of polyarylate resin (R-10-M1))
In the synthesis of polyarylate resin (R-10-M1), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-2). Further, in the synthesis of the polyarylate resin (R-10-M1), the amount of the dichloride of the compound (DC-2-1C) was changed to 54.5 mmol, and the dichloride of the compound (DC-2-2A) was used. The amount was changed to 23.3 mmol. The yield of the obtained polyarylate resin (R-10-M1) was 30.0 g, the yield was 78.9%, and the viscosity average molecular weight was 49,700.

(Synthesis of polyarylate resin (R-1-M2))
In the synthesis of polyarylate resin (R-1-M2), compound (T-M1) was changed to 0.826 mmol of compound (T-M2). The yield of the obtained polyarylate resin (R-1-M2) was 27.5 g, the yield was 79.7%, and the viscosity average molecular weight was 53,500.

(Synthesis of polyarylate resin (R-1-M3))
In the synthesis of polyarylate resin (R-1-M3), compound (T-M1) was changed to 0.826 mmol of compound (T-M3). The yield of the obtained polyarylate resin (R-1-M3) was 28.6 g, the yield was 82.9%, and the viscosity average molecular weight was 56,100.

(Synthesis of polyarylate resin (R-1-M4))
In the synthesis of polyarylate resin (R-1-M4), compound (T-M1) was changed to 0.826 mmol of compound (T-M4). The yield of the obtained polyarylate resin (R-1-M4) was 28.4 g, the yield was 82.4%, and the viscosity average molecular weight was 54,200.

(Synthesis of polyarylate resin (R-1-MA))
In the synthesis of the polyarylate resin (R-1-MA), the compound (T-M1) was converted to a compound (p-tert-butylphenol, hereinafter referred to as compound (T-MA)) represented by the following chemical formula (T-MA). may be noted) to 0.826 mmol. The viscosity average molecular weight of the polyarylate resin (R-1-MA) was 58,100.

(Synthesis of polyarylate resin (R-3-MA))
In the synthesis of polyarylate resin (R-3-MA), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-2). In the synthesis of polyarylate resin (R-3-MA), compound (T-M1) was changed to 0.826 mmol of compound (T-MA). The viscosity average molecular weight of the polyarylate resin (R-3-MA) was 55,100.

(Synthesis of polyarylate resin (R-6-MA))
In the synthesis of polyarylate resin (R-6-MA), compound (BP-1-1) was changed to 82.56 millimoles of compound (BP-1-2). Further, in the synthesis of the polyarylate resin (R-6-MA), the dichloride of the compound (DC-2-2A) was changed to 38.9 millimoles of the dichloride of the compound (DC-2-2B). In the synthesis of polyarylate resin (R-6-MA), compound (T-M1) was changed to 0.826 mmol of compound (T-MA). The viscosity average molecular weight of the polyarylate resin (R-6-MA) was 57,700.

<Production of Photoreceptor>
Photoreceptors (A-1) to (A- 22) and (B-1) to (B-17) were produced.

(Production of photoreceptor (A-1))
First, an intermediate layer was formed. A surface-treated titanium oxide (“Prototype SMT-A” manufactured by Tayca Co., Ltd., number average primary particle diameter 10 nm) was prepared. SMT-A obtains the second core by surface-treating the first core (titanium oxide core) with alumina and silica, and further surface-treats the second core with methylhydrogenpolysiloxane while wet dispersion is performed. obtained by Next, 2 parts by mass of SMT-A, and 1 part by mass of a polyamide resin ("Amilan (registered trademark) CM8000" manufactured by Toray Industries, Inc., a quaternary copolymerized polyamide resin of polyamide 6, polyamide 12, polyamide 66 and polyamide 610) , 10 parts by mass of methanol, 1 part by mass of butanol, and 1 part by mass of toluene were mixed for 5 hours using a bead mill to obtain a coating solution for forming an intermediate layer. The coating solution for forming the intermediate layer was filtered using a filter with an opening of 5 μm. Thereafter, a coating liquid for forming an intermediate layer was applied to the surface of the conductive substrate by a dip coating method. An aluminum drum-shaped support was used as the conductive substrate. Subsequently, the applied intermediate layer forming coating liquid was dried at 130° C. for 30 minutes to form an intermediate layer (thickness: 1.5 μm) on the conductive substrate.

Next, a charge generation layer was formed. Specifically, 1.5 parts by mass of Y-type titanyl phthalocyanine as a charge generating agent, 1.0 parts by mass of polyvinyl acetal resin (“S-Lec BX-5” manufactured by Sekisui Chemical Co., Ltd.) as a base resin, and 1.0 part by mass of propylene glycol monomethyl 40.0 parts by mass of ether and 40.0 parts by mass of tetrahydrofuran were mixed for 12 hours using a bead mill to obtain a coating liquid for forming a charge generation layer. The coating liquid for forming the charge generation layer was filtered using a filter with an opening of 3 μm. The resulting coating solution for forming a charge generation layer was applied onto the intermediate layer by dip coating and dried at 50° C. for 5 minutes. Thus, a charge generating layer (thickness: 0.3 μm) was formed on the intermediate layer.

Next, a charge transport layer was formed. Specifically, 45 parts by mass of a hole transport agent (HTM-1), 100 parts by mass of a polyarylate resin (R-1-M1) as a binder resin, 4 parts by mass of an azo compound (ADD-1), and an electron acceptor 2 parts by mass of compound (E-1), 550 parts by mass of tetrahydrofuran, and 150 parts by mass of toluene were mixed to obtain a coating liquid for forming a charge transport layer. The coating liquid for forming the charge transport layer was applied onto the charge generation layer by dip coating and dried at 120° C. for 40 minutes. Thus, a charge transport layer (thickness: 30 μm) was formed on the charge generation layer to obtain a photoreceptor (A-1). Photoreceptor (A-1) had an intermediate layer on the conductive substrate, a charge generation layer on the intermediate layer, and a charge transport layer on the charge generation layer.

(Production of photoreceptors (A-2) to (A-22) and (B-2) to (B-17))
The use of polyarylate resins shown in Tables 7 and 8, the use of the types of azo compounds or other compounds shown in Tables 7 and 8, and the amounts shown in Tables 7 and 8 Each of the photoreceptors (A-2) to (A-22) and (B-2) to (B-17) was prepared in the same manner as in the production of the photoreceptor (A-1), except that the compound was added. manufactured.

As already mentioned, the electron acceptor compound (E-1) and the other compound (ADD-E1) are the same compound. Since 2 parts by mass of the electron acceptor compound (E-1) and 4 parts by mass of the other compound (ADD-E1) were used in the production of the photoreceptor (B-4), a total of 6 parts by mass of the same compounds were used. That's what happened.

(Production of photoreceptor (B-1))
A photoreceptor (B-1) was produced in the same manner as the photoreceptor (A-1), except that the azo compound (ADD-1) was not added.

<Evaluation>
The following evaluations were performed for each of the photoreceptors (A-1) to (A-22) and (B-1) to (B-17) as evaluation objects.

[Evaluation of sensitivity characteristics]
The evaluation environment for the sensitivity characteristics of the photoreceptor was an environment with a temperature of 23° C. and a relative humidity of 50% RH. The surface of the photoreceptor was charged to -550 V using a drum sensitivity tester (manufactured by Gentec Co., Ltd.). Next, monochromatic light (wavelength: 780 nm, exposure amount: 1.0 μJ/cm ² ) was extracted from the light of the halogen lamp using a band-pass filter and irradiated onto the surface of the photoreceptor. The surface potential of the photoreceptor was measured when 50 milliseconds had passed since the irradiation with the monochromatic light. The measured surface potential was taken as the post-exposure potential V _L (unit: -V) of the photosensitive member. Tables 7 and 8 show the post-exposure potential V _L of each photosensitive member. The smaller the absolute value of the post-exposure potential _VL , the better the sensitivity characteristics of the photoreceptor.

[Evaluation of charging characteristics]
The evaluation environment for the charging characteristics of the photoreceptor was an environment with a temperature of 23° C. and a relative humidity of 50% RH. The surface of the photoreceptor was charged using a drum sensitivity tester (manufactured by Gentec Co., Ltd.) under the following measurement conditions. The charging conditions were such that the charging device provided in the drum sensitivity tester was a corotron charger, the charging current flowing through the corotron charger was −5 μA, the peripheral speed of the photoreceptor was 125 rpm, and static elimination was performed after charging. Met. The surface potential of the photoreceptor was measured when the photoreceptor was rotated 10 times while being charged. The measured surface potential was taken as the charging potential V ₀ (unit: -V) of the photosensitive member. Tables 7 and 8 show the charging potential V ₀ of each photoreceptor.

[Evaluation of wear resistance]
A color printer (“C711dn” manufactured by Oki Data Co., Ltd.) was used as an evaluation machine for the abrasion resistance evaluation. The toner cartridge of the evaluation machine was filled with cyan toner. First, the thickness T ₁ of the charge transport layer of the photoreceptor was measured. Next, the photoreceptor was mounted on an evaluation machine. Next, an image I (pattern image with a print rate of 1%) was printed on 10,000 sheets of paper using an evaluation machine under a normal temperature and normal humidity environment (temperature of 23° C. and relative humidity of 50% RH). Image I was printed on 10,000 sheets of paper using the evaluation machine under a high temperature and high humidity environment (temperature of 32° C. and relative humidity of 85% RH). Image I was printed on 10,000 sheets of paper using the evaluation machine under a low temperature and low humidity environment (temperature of 10° C. and relative humidity of 15% RH; hereinafter sometimes referred to as LL environment). After printing under the LL environment, the evaluation machine was allowed to stand for 2 hours. Next, a solid image (an image with an image density of 100%) was printed on a sheet of paper under the LL environment. Thereafter, the film thickness T ₂ of the charge transport layer of the photoreceptor was measured. Then, the amount of wear (T ₁ - T ₂ , unit: μm), which is the amount of change in the thickness of the charge transport layer before and after printing, was determined. The determined wear amounts are shown in Tables 7 and 8 below. Note that the smaller the amount of wear, the better the wear resistance of the photoreceptor. When the wear amount was 2.1 μm or less, the wear resistance was evaluated as good, and when the wear amount exceeded 2.1 μm, the wear resistance was evaluated as poor.

[Evaluation of light resistance to white light]
A part of the peripheral surface of the photoreceptor (10 mm long and 10 mm wide) was exposed to light with an intensity of 1000 luxm from a white fluorescent lamp ("FL40SW" manufactured by NEC Lighting Co., Ltd.) for 1 hour. The area of the peripheral surface of the photoreceptor that was exposed to light was defined as the light-exposed area. In addition, the area of the peripheral surface of the photoreceptor that was not exposed to light was defined as a non-light-exposed area. Immediately after exposure to light for 1 hour, the photoreceptor was mounted on the evaluation machine, and an evaluation machine (laser printer, Samsung "MultiXpress SL-K4350LX") was used to print image II on a sheet of paper (printing rate of 30%). halftone image) was printed. The printed image II was observed and evaluated for white light resistance according to the following criteria. Evaluation results are shown in Tables 7 and 8. When the evaluation was A or B, the light resistance to white light was evaluated as good, and when the evaluation was C, the light resistance to white light was evaluated as poor.

(Evaluation criteria for light resistance to white light)
Evaluation A: No image density difference is observed between the image area corresponding to the light-exposed area and the image area corresponding to the non-light-exposed area.
Evaluation B: A slight image density difference is observed between the image area corresponding to the light-exposed area and the image area corresponding to the non-light-exposed area.
Evaluation C: Image density difference is clearly observed between the image area corresponding to the light-exposed area and the image area corresponding to the non-light-exposed area.

The meaning of each term in Tables 7 and 8 is as follows. "Resin" indicates a polyarylate resin. "Azo etc." indicates an azo compound or other compounds. "Sensitivity" indicates evaluation of sensitivity characteristics. "Electrification" indicates evaluation of electrification characteristics. "Lightfastness" indicates evaluation of lightfastness to white light. "Parts" indicates parts by mass.

As shown in Table 7, each of photoreceptors (A-1) to (A-22) had the following construction. Specifically, the charge-generating layer contains a charge-generating agent, and the charge-transporting layer comprises a hole-transporting agent, a binder resin, and an azo compound (30) (more specifically, azo compounds (ADD-1) to (ADD -8)). The content of the azo compound (30) was 2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin. The charge transport layer contains, as a binder resin, a polyarylate resin (PA) (more specifically, polyarylate resins (R-1-M1) to (R-1-M4) and (R-2-M1) to ( 1) of R-10-M1).

Therefore, the wear amount of the photoreceptors (A-1) to (A-22) was 2.1 μm or less, and the wear resistance of these photoreceptors was good. The photoreceptors (A-1) to (A-22) were rated as "A" or "B" in light resistance to white light, and the light resistance to white light of these photoreceptors was good. .

Furthermore, the photoreceptors (A-1) to (A-22) were not only excellent in wear resistance and light resistance to white light, but also had practically usable levels without impairing sensitivity characteristics and charging characteristics. could be maintained.

From the above, it was shown that the photoreceptor according to the present invention is excellent in wear resistance and light resistance to white light.

A photoreceptor according to the present invention can be used in an image forming apparatus.

1: photoreceptor (electrophotographic photoreceptor)
2: Conductive substrate 3: Photosensitive layer 3a: Charge generation layer 3b: Charge transport layer

Claims (11)

comprising a conductive substrate and a photosensitive layer;
The photosensitive layer includes a charge generation layer and a charge transport layer,
The charge generation layer contains a charge generation agent,
The charge transport layer contains a binder resin, an azo compound represented by the general formula (30), and a hole transport agent,
The content of the azo compound represented by the general formula (30) is 2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the binder resin,
The binder resin includes a polyarylate resin having at least one type of first repeating unit, at least one type of second repeating unit, and a terminal group, and the first repeating unit is represented by general formula (1). , the second repeating unit is represented by the general formula (2), the terminal group is represented by the general formula (3) ,
The electrophotographic photoreceptor , wherein the hole transport agent contains a compound represented by the general formula (10) .

(In the general formula (30),
R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 3 carbon atoms,
Ar ¹ and Ar ² each independently represent an arylene group having 6 to 14 carbon atoms which may be substituted with at least one substituent, and the substituent is an alkyl group having 1 to 3 carbon atoms and selected from the group consisting of alkoxy groups having 1 to 3 carbon atoms,
Q represents a monovalent group represented by general formula (Q1) or (Q2). )

(In the general formula (Q1), Ar ³ and Ar ⁴ each independently represent an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms, * represents a bond, and
In general formula (Q2), Z represents a 6- to 18-membered heterocyclic ring having at least a nitrogen atom as a ring-constituting atom, and * represents a bond. )

(In the general formula (1),
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group;
R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are bonded to each other to form a divalent group represented by the general formula (X) may represent
In general formula (2), X ¹ represents a divalent group represented by chemical formula (2A), (2B), (2C), or (2D),
In the general formula (3), R ^f represents a chain aliphatic group having from 1 to 20 carbon atoms substituted with one or more fluorine atoms. )

(In the general formula (X),
t represents an integer of 1 or more and 3 or less,
* represents a bond. )

(In the general formula (10),
R ¹⁰¹ , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms represents a phenyl group optionally substituted with a group, or an alkoxy group having 1 to 8 carbon atoms, wherein adjacent two of R 103 , R ¹⁰⁴ , ^R 105 ^, R ¹⁰⁶ and R ¹⁰⁷ are bonded to form a carbon may represent a cycloalkane having from 5 to 7 atoms,
R ¹⁰² and R ¹⁰⁹ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms,
b ₁ and b ₂ each independently represent an integer of 0 or more and 5 or less. ) At least one of the first repeating units is at least one of repeating units represented by chemical formulas (1-1), (1-2), (1-3), and (1-4). 2. The electrophotographic photoreceptor according to claim 1, which is a unit.

At least one of the second repeating units is at least one of repeating units represented by chemical formulas (2-1C), (2-2A), (2-2B), and (2-2D). 3. The electrophotographic photoreceptor according to claim 1, which is a unit.

4. The electrophotographic photoreceptor according to claim 1, wherein the terminal group is represented by general formula (3-1).

(In the general formula (3-1),
R ³¹ represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms,
R ³² represents a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms,
n represents an integer of 0 or more and 2 or less. ) 5. The electrophotographic photoreceptor according to claim 1, wherein the terminal group is represented by chemical formula (M1), (M2), (M3), or (M4).

The azo compound has the chemical formulas (ADD-1), (ADD-2), (ADD-3), (ADD-4), (ADD-5), (ADD-6), (ADD-7), or ( 6. The electrophotographic photoreceptor according to any one of claims 1 to 5, represented by ADD-8).

7. The electrophotographic photoreceptor according to claim 1 , wherein the hole transport agent contains a compound represented by the chemical formula (HTM-1).

The charge transport layer further contains an electron acceptor compound,
The electrophotographic photoreceptor according to any one of claims 1 to 7 , wherein the electron acceptor compound includes a compound represented by general formula (20).

(In general formula (20), R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 6 carbon atoms.) 9. The electrophotographic photoreceptor according to claim 8 , wherein the compound represented by general formula (20) is a compound represented by chemical formula (E-1).

10. The electrophotographic photoreceptor according to claim 1 , wherein the charge transport layer does not contain titanyl phthalocyanine. The electrophotographic photoreceptor according to any one of claims 1 to 10 , wherein the charge transport layer is a single layer and provided as an outermost layer.

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