JP6763354B2 - Electrophotographic photosensitive member - Google Patents

Description

The present invention relates to an electrophotographic photosensitive member.

The electrophotographic photosensitive member is used as an image carrier in an electrophotographic image forming apparatus (for example, a printer or a multifunction device). Patent Document 1 describes an image-forming member including at least one charge transport layer containing a terphenyldiamine charge transport component having a specific structure. The terphenyldiamine charge transport component is represented by, for example, chemical formula (II).

Japanese Unexamined Patent Publication No. 2007-293342

However, according to the studies by the present inventors, it has been found that the image-forming member described in Patent Document 1 is insufficient in terms of electrical characteristics.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an electrophotographic photosensitive member capable of improving electrical characteristics and suppressing crystallization of a photosensitive layer.

The electrophotographic photosensitive member of the present invention includes a conductive substrate and a photosensitive layer. The photosensitive layer is a single layer. The photosensitive layer contains a charge generator, a hole transport agent, a binder resin, and an electron transport agent. The ratio of the mass of the hole transporting agent to the mass of the binder resin is 0.50 or more. The hole transporting agent contains a compound represented by the general formula (1).

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. ..

According to the electrophotographic photosensitive member of the present invention, it is possible to improve the electrical characteristics and suppress the crystallization of the photosensitive layer.

(A), (b) and (c) are partial cross-sectional views showing an example of an electrophotographic photosensitive member according to an embodiment of the present invention, respectively.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. The present invention can be carried out with appropriate modifications within the scope of the object of the present invention. In addition, although the description may be omitted as appropriate for the parts where the description is duplicated, the gist of the invention is not limited. Hereinafter, the compound and its derivative may be collectively referred to by adding "system" after the compound name. When the polymer name is represented by adding "system" after the compound name, it means that the repeating unit of the polymer is derived from the compound or its derivative.

Hereinafter, halogen atoms, alkyl groups having 1 to 6 carbon atoms, alkyl groups having carbon atoms to 5 or less, alkyl groups having 1 to 4 carbon atoms, alkyl groups having 1 to 3 carbon atoms, carbon atoms Alkoxy group with 1 or more and 6 or less, alkoxy group with 1 or more and 3 or less carbon atoms, aryl group with 6 or more and 14 or less carbon atoms, aryl group with 6 or more and 10 or less carbon atoms, 5 or more and 7 or less carbon atoms Cycloalkyl group, cycloalkylidene group with 5 or more and 14 or less carbon atoms, cycloalkylidene group with 5 or more and 12 or less carbon atoms, alkoxycarbonyl group with 2 or more and 7 or less carbon atoms, and alkoxycarbonyl with 2 or more and 6 or less carbon atoms Unless otherwise specified, the groups have the following meanings.

Examples of the halogen atom (halogen group) include a fluorine atom (fluoro group), a chlorine atom (chloro group), a bromine atom (bromo group) and an iodine atom (iodine group).

Alkyl groups having 1 to 6 carbon atoms, alkyl groups having 1 to 5 carbon atoms, alkyl groups having 1 to 4 carbon atoms and alkyl groups having 1 to 3 carbon atoms are linear or linear, respectively. It is branched and unsubstituted. Examples of the alkyl group having 1 or more and 6 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and isopentyl. Examples include groups, neopentyl groups, 1,2-dimethylpropyl groups, 1-ethyl-1-methylpropyl groups and hexyl groups. Examples of alkyl groups having 1 or more and 5 or less carbon atoms are groups having 1 or more and 5 or less carbon atoms among the groups described as examples of alkyl groups having 1 or more and 6 or less carbon atoms. An example of an alkyl group having 1 or more and 4 or less carbon atoms is a group having 1 or more and 4 or less carbon atoms among the groups described as examples of an alkyl group having 1 or more and 6 or less carbon atoms. An example of an alkyl group having 1 or more and 3 or less carbon atoms is a group having 1 or more and 3 or less carbon atoms among the groups described as examples of an alkyl group having 1 or more and 6 or less carbon atoms.

The alkoxy group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 3 or less carbon atoms are linear or branched and unsubstituted, respectively. Examples of the alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group and an n-pentoxy group. Examples thereof include an isopentoxy group, a neopentoxy group, a hexyloxy group and a 1-ethyl-1-methylpropoxy group. An example of an alkoxy group having 1 or more and 3 or less carbon atoms is a group having 1 or more and 3 or less carbon atoms among the groups described as examples of an alkoxy group having 1 or more and 6 or less carbon atoms.

The aryl group having 6 or more and 14 or less carbon atoms and the aryl group having 6 or more and 10 or less carbon atoms are unsubstituted. Examples of the aryl group having 6 or more carbon atoms and 14 or less carbon atoms include a phenyl group, a naphthyl group, an indacenyl group, a biphenylenyl group, an acenaphthylenyl group, an anthryl group and a phenanthryl group. Examples of the aryl group having 6 or more and 10 or less carbon atoms include a phenyl group and a naphthyl group.

Cycloalkyl groups having 5 or more and 7 or less carbon atoms are unsubstituted. Examples of the cycloalkyl group having 5 or more and 7 or less carbon atoms include a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

The cycloalkylidene group having 5 or more and 14 or less carbon atoms and the cycloalkylidene group having 5 or more and 12 or less carbon atoms are unsubstituted. Examples of the cycloalkylidene group having 5 or more and 14 or less carbon atoms include a cyclopentylidene group, a cyclohexylidene group, a cycloheptilidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, and a cycloundecylidene group. , Cyclododecylidene group, cyclotridecylidene group and cyclotetradecylidene group. A cycloalkylidene group having 5 or more and 14 or less carbon atoms is represented by the following general formula. In the general formula, t represents an integer of 1 or more and 10 or less, and * represents a bond. t preferably represents an integer of 1 or more and 8 or less, more preferably 1, 2 or 8, and even more preferably 2 or 8.

The alkoxycarbonyl group having 2 or more and 7 or less carbon atoms and the alkoxycarbonyl group having 2 or more and 6 or less carbon atoms are linear or branched and unsubstituted, respectively. An alkoxycarbonyl group having 2 or more and 7 or less carbon atoms is a carbonyl group having an alkyl group having 1 or more and 6 or less carbon atoms. The alkoxycarbonyl group having 2 or more and 6 or less carbon atoms is a carbonyl group having an alkyl group having 1 or more and 5 or less carbon atoms.

<Electrophotophotoreceptor>
The present embodiment relates to an electrophotographic photosensitive member (hereinafter, may be referred to as a photosensitive member). Hereinafter, the photoconductor 1 according to the present embodiment will be described with reference to FIG. FIG. 1 is a partial cross-sectional view showing an example of the photoconductor 1 according to the present embodiment.

As shown in FIG. 1A, the photoconductor 1 includes, for example, a conductive substrate 2 and a photosensitive layer 3. The photosensitive layer 3 is a single layer. The photoconductor 1 is a single-layer electrophotographic photosensitive member including a single-layer photosensitive layer 3.

As shown in FIG. 1B, the photoconductor 1 may include a conductive substrate 2, a photosensitive layer 3, and an intermediate layer 4 (undercoat layer). The intermediate layer 4 is provided between the conductive substrate 2 and the photosensitive layer 3. As shown in FIG. 1A, the photosensitive layer 3 may be provided directly on the conductive substrate 2. Alternatively, as shown in FIG. 1B, the photosensitive layer 3 may be provided on the conductive substrate 2 via the intermediate layer 4.

As shown in FIG. 1 (c), the photoconductor 1 may include a conductive substrate 2, a photosensitive layer 3, and a protective layer 5. The protective layer 5 is provided on the photosensitive layer 3.

The thickness of the photosensitive layer 3 is not particularly limited, but is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. The photoconductor 1 has been described above with reference to FIG. Hereinafter, the photoconductor will be described in more detail.

<Photosensitive layer>
The photosensitive layer contains a charge generator, a hole transport agent, a binder resin, and an electron transport agent. The photosensitive layer may contain additives, if necessary.

(Hole transport agent)
The hole transporting agent includes a compound represented by the following general formula (1) (hereinafter, may be referred to as compound (1)). The photosensitive layer contains compound (1) as a hole transport agent.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group.

By containing the compound (1) in the photosensitive layer, the electrical characteristics of the photoconductor (for example, one or both of the sensitivity characteristics and the charging characteristics) can be improved, and the crystallization of the photosensitive layer can be suppressed. .. The reason is presumed as follows.

First, in the general formula (1), a methoxy group is bonded to the para position of the phenyl group to which R ^{1 to} R ¹⁰ are not bonded (hereinafter, may be referred to as phenyl group A). As a result, the sensitivity characteristics of the photoconductor can be improved and the crystallization of the photosensitive layer can be suppressed. On the contrary, when a substituent other than the methoxy group (for example, an alkyl group or a hydrogen atom) is bonded to the para position of the phenyl group A, the sensitivity characteristics of the photoconductor are lowered. Further, if a substituent other than the methoxy group (for example, an alkyl group or a hydrogen atom) is bonded to the para position of the phenyl group A, the crystallization of the photosensitive layer cannot be suppressed. Further, when the methoxy group is bonded to a position other than the para position (for example, the ortho position or the meta position) of the phenyl group A, the sensitivity characteristic of the photoconductor is lowered.

Second, in the general formula (1), a hydrogen atom is bonded to the ortho-position and the meta-position of the phenyl group A. As a result, the sensitivity characteristics of the photoconductor can be improved. On the contrary, when a substituent other than a hydrogen atom (for example, an alkyl group) is bonded to one or more of the ortho-position and the meta-position of the phenyl group A, the sensitivity characteristics of the photoconductor are lowered.

Third, in the general formula (1), R ^{1 to} R ¹⁰ each independently represent a hydrogen atom or a methyl group. As a result, the sensitivity characteristics of the photoconductor can be improved. On the contrary, when R ^{1 to} R ¹⁰ are alkyl groups having 2 or more carbon atoms, the sensitivity characteristics of the photoconductor deteriorate.

Next, as a preferable example of the compound (1), the compounds represented by the chemical formulas (1-1), (1-2) and (1-3) (hereinafter, each of the compounds (1-1), (1), It may be described as 1-2) and (1-3)). In order to further improve the sensitivity characteristics of the photoconductor while suppressing the crystallization of the photosensitive layer, more preferable examples of the compound (1) include compounds (1-2) and (1-3).

The ratio of the mass m _HTM of the hole transporting agent to the mass m _{Resin of the} binder resin m _HTM / m _Resin is 0.50 or more. If the ratio m _HTM / m _Resin is less than 0.50, the sensitivity characteristics of the photoconductor deteriorate. In order to improve the sensitivity characteristics of the photoconductor, the ratio m _HTM / m _Resin is more preferably 0.55 or more. The upper limit of the ratio m _HTM / m _Resin can be, for example, 0.70.

When the photosensitive layer contains only the compound (1) as the hole transporting agent, the mass m _HTM of the hole transporting agent is the mass of the compound (1). When the photosensitive layer contains two or more kinds of hole transporting agents, the mass m _HTM of the hole transporting agents is the sum of the masses of the two or more kinds of hole transporting agents.

When the photosensitive layer contains one kind of binder resin, the mass m _Resin of the binder resin is the mass of one kind of binder resin. When the photosensitive layer contains two or more kinds of binder resins, the mass m _Resin of the binder resin is the sum of the masses of the two or more kinds of binder resins.

The photosensitive layer may contain only one kind of compound (1), or may contain two or more kinds of compound (1). Further, the photosensitive layer may contain only compound (1) as a hole transporting agent. Further, the photosensitive layer may further contain other hole transporting agents in addition to the compound (1).

As the other hole transporting agent, for example, a nitrogen-containing cyclic compound other than the compound (1) or a condensed polycyclic compound can be used. Examples of the nitrogen-containing ring compound and the condensed polycyclic compound other than the compound (1) include diamine compounds (for example, N, N, N', N'-tetraphenylphenylenediamine derivatives, N, N, N', N'-tetraphenylnaphthylene diamine derivative or N, N, N', N'-tetraphenylphenanthrylene diamine derivative), oxadiazole-based compound (for example, 2,5-di (4-methylaminophenyl)- 1,3,4-oxadiazol), styryl compounds (eg 9- (4-diethylaminostyryl) anthracene), carbazole compounds (eg polyvinylcarbazole), organic polysilane compounds, pyrazoline compounds (eg 1-phenyl- 3- (p-Dimethylaminophenyl) pyrazoline), hydrazone compounds, indol compounds, oxazole compounds, isooxazole compounds, thiazole compounds, thiadiazol compounds, imidazole compounds, pyrazole compounds and triazole compounds. ..

(Binder resin)
Examples of the binder resin contained in the photosensitive layer include thermoplastic resins, thermosetting resins and photocurable resins. Examples of the thermoplastic resin include polyarylate resins, polycarbonate resins, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, acrylic acid polymers, and styrene-acrylic acid copolymers. Polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide resin, urethane resin, polysulfone resin, diallyl phthalate Examples thereof include resins, ketone resins, polyvinyl butyral resins, polyester resins and polyether resins. Examples of the thermosetting resin include silicone resin, epoxy resin, phenol resin, urea resin and melamine resin. Examples of the photocurable resin include an acrylic acid adduct of an epoxy compound and an acrylic acid adduct of a urethane compound. The photosensitive layer may contain only one of these binder resins, or may contain two or more of these binder resins.

The viscosity average molecular weight of the binder resin is preferably 10,000 or more, more preferably 20,000 or more, further preferably 30,000 or more, and particularly preferably 40,000 or more. .. When the viscosity average molecular weight of the binder resin is 10,000 or more, the abrasion resistance of the binder resin is enhanced and the photosensitive layer is less likely to be worn. On the other hand, the viscosity average molecular weight of the binder resin is preferably 80,000 or less, and more preferably 70,000 or less. When the viscosity average molecular weight of the binder resin is 80,000 or less, the binder resin is easily dissolved in the solvent for forming the photosensitive layer, and the photosensitive layer is easily formed.

A polyarylate resin or a polycarbonate resin is preferable as the binder resin in order to further improve the sensitivity characteristics of the photoconductor and further suppress the crystallization of the photosensitive layer.

(Polyarylate resin)
In order to further improve the sensitivity characteristics of the photoconductor and further suppress the crystallization of the photosensitive layer, the polyarylate resin includes at least one type of repeating unit represented by the general formula (10) and the general formula (11). A polyarylate resin containing at least one of the repeating units represented by is preferable. Hereinafter, the repeating units represented by the general formulas (10) and (11) may be described as repeating units (10) and (11), respectively.

In the general formula (10), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group. R ¹³ represents a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms, and R ¹⁴ represents an alkyl group having 1 or more and 4 or less carbon atoms. Alternatively, R ¹³ and R ¹⁴ are bonded to each other to represent a cycloalkylidene group having 5 or more and 14 or less carbon atoms.

When the polyarylate resin contains one kind of repeating unit (11), in the general formula (11), X represents a divalent group represented by the chemical formula (X1).

When the polyarylate resin contains at least two repeating units (11), in the general formula (11), X is a chemical formula (X1), a chemical formula (X2), a chemical formula (X3), a chemical formula (X4), a chemical formula (X4). Represents a divalent group represented by X5) or the chemical formula (X6). In one of the repeating units (11) of at least two repeating units (11), X in the general formula (11) represents a divalent group represented by the chemical formula (X1). In the repeating unit (11) of at least two kinds of repeating units (11), X in the general formula (11) is a chemical formula (X2), a chemical formula (X3), a chemical formula (X4), a chemical formula (X4). Represents a divalent group represented by X5) or the chemical formula (X6).

(Repeating unit (10))
The repeating unit (10) will be described. In the general formula (10), the alkyl group represented by R ¹³ and R ¹⁴ having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group.

In the general formula (10), the cycloalkylidene group having 5 or more and 14 or less carbon atoms represented by the bonds of R ¹³ and R ¹⁴ to each other is preferably a cycloalkylidene group having 5 or more and 12 or less carbon atoms, and is a cyclopentylidene group. , Cyclohexylidene group or cyclododecylidene group is more preferable, and cyclohexylidene group or cyclododecylidene group is further preferable.

Preferable examples of the repeating unit (10) include repeating units represented by the chemical formulas (10-1), (10-2), (10-3) and (10-4). Hereinafter, the repeating units represented by the chemical formulas (10-1), (10-2), (10-3) and (10-4) are referred to as repeating units (10-1), (10-2), respectively. It may be described as (10-3) and (10-4). In order to further suppress the crystallization of the photosensitive layer while improving the sensitivity characteristics of the photoconductor, more preferable examples of the repeating unit (10) are the repeating unit (10-1), (10-2) and (10-3) can be mentioned.

The polyarylate resin may contain only one type of repeating unit (10) as the repeating unit (10), and may contain at least two types (for example, two or three types) of the repeating unit (10). May be good.

Next, the repeating unit (11) will be described separately for the case where the polyarylate resin contains one kind of repeating unit (11) and the case where at least two kinds of repeating units (11) are contained.

(When one type of repeating unit (11) is included)
When the polyarylate resin contains one kind of repeating unit (11), in the general formula (11), X represents a divalent group represented by the chemical formula (X1). In this case, the polyarylate resin contains at least one type of repeating unit (10) and a repeating unit represented by the chemical formula (11-X1) (hereinafter, may be referred to as a repeating unit (11-X1)). Including. In this case, the polyarylate resin preferably contains one type of repeating unit (10) and a repeating unit (11-X1).

(When at least two repeating units (11) are included)
When the polyarylate resin contains at least two repeating units (11), in the general formula (11), X is a chemical formula (X1), a chemical formula (X2), a chemical formula (X3), a chemical formula (X4), a chemical formula (X4). Represents a divalent group represented by X5) or the chemical formula (X6). In one of the repeating units (11) of at least two repeating units (11), X in the general formula (11) represents a divalent group represented by the chemical formula (X1). In this case, the polyarylate resin includes at least one of the repeating unit (10), the repeating unit (11-X1), and the repeating unit represented by the general formula (11') (hereinafter, the repeating unit (11'). Includes at least one of the). In this case, the polyarylate resin preferably contains one type of repeating unit (10), one type of repeating unit (11-X1), and one type of repeating unit (11').

X'in the general formula (11') represents a divalent group represented by the chemical formulas (X2), (X3), (X4), (X5) or (X6). X'preferably represents a divalent group represented by the chemical formula (X2) or (X3).

Examples of the repeating unit (11') are the repeating units represented by the chemical formulas (11-X2), (11-X3), (11-X4), (11-X5) and (11-X6) (hereinafter,). Each may be described as a repeating unit (11-X2), (11-X3), (11-X4), (11-X5) and (11-X6)). As the repeating unit (11'), the repeating unit (11-X2) or (11-X3) is preferable.

In order to improve the sensitivity characteristics of the photoconductor and suppress the crystallization of the photosensitive layer, the polyarylate resin preferably contains at least two types of repeating units (11), and two or more types of repeating units (11). It is more preferable to include 8 or less, more preferably 2 or 3 of the repeating unit (11), and particularly preferably 2 of the repeating unit (11).

In order to improve the sensitivity characteristics of the photoconductor and suppress the crystallization of the photosensitive layer, the repeating unit (11-X1) with respect to the sum of the number of repeating units (11-X1) and the number of repeating units (11') The ratio of the number of) (hereinafter, may be referred to as ratio p) is preferably 0.10 or more and 0.90 or less, more preferably 0.20 or more and 0.80 or less, and 0. It is more preferably 30 or more and 0.70 or less, further preferably 0.40 or more and 0.60 or less, and particularly preferably 0.50. The ratio p is not a value obtained from one molecular chain, but an average value obtained from the entire polyarylate resin (plurality of molecular chains) contained in the photosensitive layer. The ratio p can be calculated from the ¹ H-NMR spectrum obtained by measuring the ¹ H-NMR spectrum of the polyarylate resin using a proton nuclear magnetic resonance spectrometer.

In order to further suppress the crystallization of the photosensitive layer while improving the sensitivity characteristics of the photoconductor, a polyallylate resin containing at least one of the repeating unit (10) and at least one of the repeating unit (11) is suitable. Examples include polyallylate resins comprising repeating units (10-1), repeating units (11-X1) and repeating units (11-X3); repeating units (10-2), repeating units (11-X1) and Polyallylate resin containing repeating unit (11-X3); polyallylate resin containing repeating unit (10-2), repeating unit (11-X1) and repeating unit (11-X2); and repeating unit (10-3) , Polyarylate resin containing a repeating unit (11-X1) and a repeating unit (11-X3).

Examples of the polyarylate resin containing at least one of the repeating unit (10) and at least one of the repeating unit (11) include a polyarylate resin containing the repeating unit (10-4) and the repeating unit (11-X3). May be used.

In the polyarylate resin, the repeating unit derived from the aromatic diol and the repeating unit derived from the aromatic dicarboxylic acid are adjacent to each other and bonded to each other. When the polyarylate resin is a copolymer, the polyarylate resin may be, for example, a random copolymer, an alternating copolymer, a periodic copolymer or a block copolymer.

The repeating unit derived from the aromatic diol is, for example, the repeating unit (10). When the polyarylate resin contains two or more kinds of repeating units (10), the arrangement of one kind of repeating unit (10) and another kind of repeating unit (10) is not particularly limited. One type of repeating unit (10) and another type of repeating unit and (10) can be arranged randomly, alternately, periodically or block by block via the repeating unit (11). The repeating unit derived from the aromatic dicarboxylic acid is, for example, the repeating unit (11). When the polyarylate resin contains two or more kinds of repeating units (11), the arrangement of one kind of repeating unit (11) and another kind of repeating unit (11) is not particularly limited. One type of repeating unit (11) and another type of repeating unit (11) can be arranged randomly, alternately, periodically or block by block via the repeating unit (10).

The polyarylate resin may contain only the repeating units (10) and (11) as the repeating unit. Further, the polyarylate resin may further contain repeating units other than the repeating units (10) and (11) in addition to the repeating units (10) and (11).

The photosensitive layer may contain only one type of polyarylate resin containing at least one type of repeating unit (10) and at least one type of repeating unit (11) as a binder resin, and such a polyarylate may be contained. Two or more kinds of resins may be contained. Further, in the photosensitive layer, in addition to the polyarylate resin containing at least one of the repeating unit (10) and at least one of the repeating unit (11) as the binder resin, other binder resins are further contained. May be good.

The method for producing the polyarylate resin is not particularly limited. Examples of the method for producing a polyarylate resin include a method of polycondensing an aromatic diol for forming a repeating unit and an aromatic dicarboxylic acid for forming a repeating unit. As a method for polycondensation, a known synthesis method (more specifically, solution polymerization, melt polymerization, interfacial polymerization, etc.) can be adopted.

The aromatic diol for constituting the repeating unit is, for example, at least one of the compounds represented by the general formula (BP-10). The aromatic dicarboxylic acid for constituting the repeating unit is, for example, at least one of the compounds represented by the general formula (DC-11). Formula (BP-10) and R ¹¹ of (DC-11) in, R ^12, R ^13, R ¹⁴ and X are each, R ¹¹ in formula (10) and (11) in, R ^12, R It is synonymous with ¹³ , R ¹⁴ and X. Hereinafter, the compounds represented by the general formulas (BP-10) and (DC-11) may be referred to as compounds (BP-10) and (DC-11), respectively.

Preferable examples of the compound (BP-10) are the compounds represented by the chemical formulas (BP-10-1) to (BP-10-4) (hereinafter, each of the compounds (BP-10-1) to (BP). -10-4) may be described).

Preferable examples of the compound (DC-11) are the chemical formulas (DC-11-X1) to (DC-11-X6) (hereinafter, each of the compounds (DC-11-X1) to (DC-11-X6)). May be described).

Aromatic diols (eg, compound (BP-10)) for forming repeating units may be transformed into aromatic diacetates for use. Aromatic dicarboxylic acids (eg, compound (DC-11)) for constructing repeating units may be derivatized and used. Examples of derivatives of aromatic dicarboxylic acids include aromatic dicarboxylic acid dichloride, aromatic dicarboxylic acid dimethyl ester, aromatic dicarboxylic acid diethyl ester and aromatic dicarboxylic acid anhydride. Aromatic dicarboxylic acid dichloride is a compound in which two "-C (= O) -OH" groups of an aromatic dicarboxylic acid are each replaced with a "-C (= O) -Cl" group.

In the polycondensation of the aromatic diol and the aromatic dicarboxylic acid, one or both of the base and the catalyst may be added. The base and catalyst can be appropriately selected from known bases and catalysts. Examples of bases include sodium hydroxide. Examples of catalysts include benzyltributylammonium chloride, ammonium chloride, ammonium bromide, quaternary ammonium salts, triethylamine and trimethylamine. The polyarylate resin has been described above.

(Polycarbonate resin)
In order to further improve the sensitivity characteristics of the photoconductor and further suppress the crystallization of the photosensitive layer, the polycarbonate resin is repeatedly represented by the chemical formulas (R-5), (R-6) or (R-7). Polycarbonate resin containing a unit is preferable. Hereinafter, the repeating units represented by the chemical formulas (R-5), (R-6) and (R-7) are referred to as repeating units (R-5), (R-6) and (R-7), respectively. May be described.

In order to suppress the crystallization of the photosensitive layer while improving the sensitivity characteristics of the photoconductor, suitable examples of the polycarbonate resin include a polycarbonate resin containing a repeating unit (R-5) and a repeating unit (R-6). Examples include polycarbonate resin containing.

As the binder resin, only one kind of polycarbonate resin containing a repeating unit (R-5), (R-6) or (R-7) may be contained, and two or more kinds of such polycarbonate resins are contained. You may. Further, as the binder resin, in addition to the polycarbonate resin containing the repeating unit (R-5), (R-6) or (R-7), other binder resins may be further contained. The polycarbonate resin has been described above.

(Electronic transport agent)
The photosensitive layer contains an electron transporting agent. Since the photosensitive layer contains an electron transporting agent, it is possible to improve the sensitivity characteristics of the photoconductor while suppressing the crystallization of the photosensitive layer. Further, it is considered that when the electron transporting agent forms a complex with the compound (1), the formed complex is suitably dissolved in the solvent for forming the photosensitive layer. As a result, a uniform photosensitive layer is easily formed, the sensitivity characteristics of the photoconductor are further improved, and crystallization of the photosensitive layer is further suppressed.

The ratio of the mass m _ETM of the electron transporting agent to the mass m _HTM of the hole transporting agent m _ETM / m _HTM is preferably 0.01 or more and 1.50 or less. When the ratio m _ETM / m _HTM is 0.01 or more, the sensitivity characteristics of the photoconductor can be further improved. When the ratio m _ETM / m _HTM is 1.50 or less, the sensitivity characteristics of the photoconductor can be further improved, and the crystallization of the photosensitive layer can be further suppressed. In order to further improve the sensitivity characteristics of the photoconductor while suppressing the crystallization of the photosensitive layer, the ratio m _ETM / m _HTM is more preferably 0.40 or more, and more preferably 0.50 or more. More preferably, it is more preferably 0.60 or more. In order to further improve the sensitivity characteristics of the photoconductor while suppressing the crystallization of the photosensitive layer, the ratio m _ETM / m _HTM is more preferably 1.00 or less, and preferably 0.70 or less. More preferred. When the photosensitive layer contains two or more kinds of electron transporting agents, the mass m _ETM of the electron transporting agent is the sum of the masses of the two or more kinds of electron transporting agents. When the photosensitive layer contains two or more kinds of hole transporting agents, the mass m _HTM of the hole transporting agents is the sum of the masses of the two or more kinds of hole transporting agents.

In order to improve the sensitivity characteristics of the photoconductor, the ratio of the sum of the mass m _HTM of the hole transporting agent and the mass m _ETM of the electron transporting agent to the mass m _Resin of the binder resin (m _HTM + m _ETM ) / m _Resin is , 0.55 or more, more preferably 0.65 or more, further preferably 0.75 or more, further preferably 0.80 or more, and more preferably 0.85 or more. Is even more preferable, and 1.00 or more is particularly preferable. The upper limit of the ratio (m _HTM + m _ETM ) / m _Resin can be, for example, 1.70.

Examples of the electron transporting agent include quinone compounds, diimide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds, and the like. Examples thereof include dinitroanthracene-based compounds, dinitroacridine-based compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroaclydin, succinic anhydride, maleic anhydride and dibromomaleic anhydride. Examples of the quinone compound include diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds and dinitroanthraquinone compounds. One kind of electron transporting agent may be contained, or two or more kinds of electron transporting agents may be contained.

Preferable examples of the electron transporting agent include compounds represented by the general formulas (20), (21), (22), (23) and (24) (hereinafter, each of the compounds (20) and (21)). , (22), (23) and (24)). When the electron transporting agent is compound (20), (21), (22), (23) or (24), the electron transporting agent tends to preferably form a complex with compound (1). Therefore, it is considered that the formed complex is preferably dissolved in the solvent for forming the photosensitive layer. As a result, a uniform photosensitive layer is easily formed, the sensitivity characteristics of the photoconductor are further improved, and crystallization of the photosensitive layer is further suppressed.

In the general formula (20), Q ¹ , Q ² , Q ³ and Q ⁴ are independently alkyl groups having 1 or more and 6 or less carbon atoms, alkoxy groups having 1 or more and 6 or less carbon atoms, and 5 carbon atoms. It represents a cycloalkyl group of 7 or more or an aryl group having 6 or more carbon atoms and 14 or less. In the general formula (21), Q ¹¹ and Q ¹² are independently an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, and a cycloalkyl having 5 or more and 7 or less carbon atoms. It represents a group or an aryl group having 6 or more and 14 or less carbon atoms. In the general formula (22), Q ²¹ and Q ²² may independently have an alkyl group having 1 or more and 6 or less carbon atoms or an alkoxy group having 1 or more and 6 or less carbon atoms, each having 6 carbon atoms. It represents 14 or more aryl groups. In the general formula (23), Q ³¹ represents an alkoxycarbonyl group having 2 to 7 carbon atoms. In the general formula (24), Q ⁴¹ and Q ⁴² each independently represent an alkyl group having 1 to 6 carbon atoms, and Q ⁴³ represents a halogen atom.

The number of carbon atoms represented by Q ¹ , Q ² , Q ³ and Q ^{4 in} the general formula (20), Q ¹¹ and Q ¹² in the general formula (21), and Q ⁴¹ and Q ⁴² in the general formula (24). As the alkyl group of 1 or more and 6 or less, a methyl group, an ethyl group, a butyl group or a hexyl group is preferable, and a methyl group, a tert-butyl group or a 1-ethyl-1-methylpropyl group is more preferable.

The alkoxy group having 1 or more and 6 or less carbon atoms represented by Q ¹ , Q ² , Q ³ and Q ^{4 in} the general formula (20) and Q ¹¹ and Q ¹² in the general formula (21) has the number of carbon atoms. Alkoxy groups of 1 or more and 3 or less are preferable.

The cycloalkyl groups represented by Q ¹ , Q ² , Q ³ and Q ^{4 in} the general formula (20) and Q ¹¹ and Q ¹² in the general formula (21) have 5 to 7 carbon atoms and are cyclohexyl groups. Is preferable.

The number of carbon atoms represented by Q ¹ , Q ² , Q ³ and Q ^{4 in} the general formula (20), Q ¹¹ and Q ^{12 in} the general formula ( ²¹ ), and Q ²¹ and Q ²² in the general formula (22) is 6. As the aryl group having 14 or less, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is more preferable.

The aryl group having 6 or more and 14 or less carbon atoms represented by Q ²¹ and Q ²² in the general formula (22) is an alkyl group having 1 or more and 6 or less carbon atoms or an alkoxy having 1 or more carbon atoms and 6 or less carbon atoms as a substituent. It may have a group. As such a substituent, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable. The number of substituents (specifically, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms) represented by Q ²¹ and Q ²² and having an aryl group having 6 to 14 carbon atoms. Is preferably 1 or more and 3 or less, and more preferably 2.

As the alkoxycarbonyl group having 2 to 7 carbon atoms represented by Q ³¹ in the general formula (23), a butoxycarbonyl group is preferable, and an n-butoxycarbonyl group is more preferable.

As the halogen atom represented by Q ⁴³ in the general formula (24), a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable.

In the general formula (20), Q ¹ , Q ² , Q ³ and Q ⁴ each independently preferably represent an alkyl group having 1 or more and 6 or less carbon atoms. In the general formula (21), Q ¹¹ and Q ¹² each independently preferably represent an alkyl group having 1 or more and 6 or less carbon atoms. In the general formula (22), Q ²¹ and Q ²² each independently preferably represent an aryl group having 6 to 14 carbon atoms and having an alkyl group having 1 to 6 carbon atoms. In the general formula (23), Q ³¹ preferably represents an alkoxycarbonyl group having 2 or more and 6 or less carbon atoms. In the general formula (24), Q ⁴¹ and Q ⁴² each independently represent an alkyl group having 1 or more and 4 or less carbon atoms, and Q ⁴³ preferably represents a chlorine atom.

The compounds represented by the chemical formulas (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) and (24-E6) are preferably used as the electron transporting agent (hereinafter referred to as “2”). , Each of which may be referred to as compound (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) and (24-E6)). .. Preferable examples of compound (20) include compounds (20-E1) and (20-E2). Preferable examples of compound (21) include compound (21-E3). Preferable examples of compound (22) include compound (22-E4). Preferable examples of compound (23) include compound (23-E5). Preferable examples of compound (24) include compound (24-E6).

As the electron transporting agent, the photosensitive layer may contain only one of the compounds (20), (21), (22), (23) and (24), or the photosensitive layer may contain two or more compounds. Good. In addition to the compounds (20) to (24), the photosensitive layer may contain an electron transporting agent other than the compounds (20) to (24).

Further, as the electron transporting agent, only one of the compounds (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) and (24-E6) is used as the photosensitive layer. May be contained, or two or more kinds may be contained in the photosensitive layer. Further, in addition to the compounds (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) and (24-E6), other electron transporting agents are exposed to light. The layer may contain.

(Charge generator)
Examples of the charge generator include phthalocyanine pigments, perylene pigments, bisazo pigments, trisazo pigments, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaline pigments, indigo pigments, azulenium pigments, and cyanine. Pigments, powders of inorganic photoconductive materials (eg, selenium, selenium-tellu, selenium-arsenic, cadmium sulfide or amorphous silicon), pyrylium pigments, anthanthrone pigments, triphenylmethane pigments, slen pigments, toluidine pigments, Examples thereof include pyrazoline pigments and quinacridone pigments. The photosensitive layer may contain only one type of charge generating agent, or may contain two or more types.

Examples of the phthalocyanine pigment include metal-free phthalocyanine and metal phthalocyanine. Examples of the metallic phthalocyanine include titanyl phthalocyanine, hydroxygallium phthalocyanine and chlorogallium phthalocyanine. Metal-free phthalocyanines are represented by the chemical formula (CGM-1). Titanyl phthalocyanine is represented by the chemical formula (CGM-2).

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

For example, it is preferable to use a photoconductor 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 a facsimile using a light source such as a semiconductor laser). Since it has a high quantum yield in the wavelength region of 700 nm or more, the phthalocyanine pigment is preferable, the metal-free phthalocyanine or titanyl phthalocyanine is more preferable, and the X-type metal-free phthalocyanine or Y-type titanyl phthalocyanine is further preferable. , Y-type titanyl phthalocyanine is particularly preferable.

Ansanthron pigments are preferably used as the charge generator in the photoconductor applied to an image forming apparatus using a short wavelength laser light source (for example, a laser light source having a wavelength of 350 nm or more and 550 nm or less).

The content of the charge generator is preferably 0.1 part by mass or more and 50 parts by mass or less, and 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the photosensitive layer. It is more preferable that the amount is 0.5 parts by mass or more and 4.5 parts by mass or less.

(Additive)
Additives include, for example, antioxidants (eg, antioxidants, radical scavengers, singlet quenchers or UV absorbers), softeners, surfactants, bulking agents, thickeners, dispersion stabilizers. , Wax, donor, surfactant, plasticizer, sensitizer and leveling agent. Antioxidants include, for example, hindered phenol (eg, di (tert-butyl) p-cresol), hindered amines, para-phenylenediamine, aryl alkanes, hydroquinone, spirochroman, spiroidanone and derivatives thereof. Examples of the antioxidant include organic sulfur compounds and organic phosphorus compounds. Examples of the leveling agent include dimethyl silicone oil. Examples of the sensitizer include metaterphenyl.

(Combination of materials)
In order to further improve the sensitivity characteristics of the photoconductor and further suppress the crystallization of the photosensitive layer, the hole transporting agent, the binder resin and the electron transporting agent are preferably in the following combinations. Further, it is more preferable that the hole transporting agent, the binder resin and the electron transporting agent are the following combinations, and the charge generating agent is Y-type titanyl phthalocyanine.

The hole transport agent is a compound (1-1), and the binder resin is a polyarylate resin containing a repeating unit (10-1), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is compound (1-2), and the binder resin is a polyarylate resin containing a repeating unit (10-1), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is a compound (1-3), and the binder resin is a polyarylate resin containing a repeating unit (10-1), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-1), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is the compound (1-2), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is a compound (1-3), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is compound (1-1), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X2), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is a compound (1-2), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X2), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is a compound (1-3), and the binder resin is a polyarylate resin containing a repeating unit (10-2), a repeating unit (11-X1), and a repeating unit (11-X2), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is the compound (1-1), and the binder resin is a polyarylate resin containing a repeating unit (10-3), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-2), and the binder resin is a polyarylate resin containing a repeating unit (10-3), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is a compound (1-3), and the binder resin is a polyarylate resin containing a repeating unit (10-3), a repeating unit (11-X1), and a repeating unit (11-X3), and is an electron. Is the transport agent (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-1), the binder resin is a polyarylate resin containing a repeating unit (10-4) and a repeating unit (11-X3), and the electron transporting agent is (20-E1). , (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-2), the binder resin is a polyarylate resin containing a repeating unit (10-4) and a repeating unit (11-X3), and the electron transporting agent is (20-E1). , (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-3), the binder resin is a polyarylate resin containing a repeating unit (10-4) and a repeating unit (11-X3), and the electron transporting agent is (20-E1). , (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6);
The hole transporting agent is compound (1-1), the binder resin is a polycarbonate resin containing a repeating unit (R-5), and the electron transporting agent is (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-2), the binder resin is a polycarbonate resin containing a repeating unit (R-5), and the electron transport agent is (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-3), the binder resin is a polycarbonate resin containing a repeating unit (R-5), and the electron transport agent is (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-1), the binder resin is a polycarbonate resin containing a repeating unit (R-6), and the electron transport agent is (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is compound (1-2), the binder resin is a polycarbonate resin containing a repeating unit (R-6), and the electron transporters are (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transporter is compound (1-3), the binder resin is a polycarbonate resin containing a repeating unit (R-6), and the electron transporters are (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transport agent is compound (1-1), the binder resin is a polycarbonate resin containing a repeating unit (R-7), and the electron transport agent is (20-E1), (20-E2), (21-). Is it E3), (22-E4), (23-E5) or (24-E6);
The hole transporting agent is the compound (1-2), the binder resin is a polycarbonate resin containing a repeating unit (R-7), and the electron transporting agent is (20-E1), (20-E2), (21-). E3), (22-E4), (23-E5) or (24-E6); or the hole transporter is compound (1-3) and the binder resin is the repeating unit (R-7). It is a polycarbonate resin containing, and the electron transporting agent is (20-E1), (20-E2), (21-E3), (22-E4), (23-E5) or (24-E6).

<Conductive substrate>
The conductive substrate is not particularly limited as long as it can be used as the conductive substrate of the photoconductor. The conductive substrate may be made of a material having a conductive surface at least. An example of a conductive substrate is a conductive substrate made of a conductive material. Another example of a conductive substrate is a conductive substrate coated with a conductive material. Examples of the conductive material include 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 in combination of two or more (for example, as an alloy). Among these conductive materials, aluminum and aluminum alloys are preferable because the transfer of charge from the photosensitive layer to the conductive substrate is good.

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. The thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.

<Mesosphere>
The intermediate layer (undercoat layer) contains, for example, inorganic particles and a resin used for the intermediate layer (resin for the intermediate layer). It is considered that the presence of the intermediate layer facilitates the flow of current generated when the photoconductor is exposed while maintaining an insulating state to the extent that leakage can be suppressed, and suppresses an increase in resistance.

Inorganic particles include, for example, metal (eg, aluminum, iron or copper), metal oxide (eg, titanium oxide, alumina, zirconium oxide, tin oxide or zinc oxide) particles and non-metal oxide (eg, silica). Particles can be mentioned. One type of these inorganic particles may be used alone, or two or more types may be used in combination.

The example of the resin for the intermediate layer is the same as the example of the other binder resin described above. In order to form the intermediate layer and the photosensitive layer well, it is preferable that the resin for the intermediate layer is different from the binder resin contained in the photosensitive layer. The intermediate layer may contain additives. The example of the additive contained in the intermediate layer is the same as the example of the additive contained in the photosensitive layer.

<Manufacturing method of photoconductor>
An example of a method for manufacturing a photoconductor will be described. The method for producing a photoconductor includes, for example, a step of forming a photosensitive layer. In the photosensitive layer forming step, a coating liquid for forming the photosensitive layer (hereinafter, may be referred to as a coating liquid) is prepared. The coating liquid is applied onto the conductive substrate. Next, at least a part of the solvent contained in the applied coating liquid is removed to form a photosensitive layer. The coating liquid contains, for example, a charge generator, compound (1), a binder resin, an electron transporting agent, and a solvent. The coating liquid is prepared by dissolving or dispersing the charge generator, the compound (1), the binder resin, and the electron transporting agent in a solvent. The coating liquid may contain an additive if necessary.

The solvent contained in the coating liquid is not particularly limited as long as each component contained in the coating liquid can be dissolved or dispersed. Examples of the solvent include alcohol (more specifically, methanol, ethanol, isopropanol or butanol, etc.), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, etc.), aromatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, etc.) More specifically, benzene, toluene, xylene, etc.), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.), ethers (more specifically, dimethyl ether, diethyl ether, etc.), Tetrahydrofuran, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, etc.), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (more specifically, ethyl acetate, methyl acetate, etc.), dimethylformaldehyde, dimethylformamide, and Examples include dimethylsulfoxide. These solvents may be used alone or in combination of two or more. Of these solvents, it is preferable to use a non-halogenated solvent (solvent other than halogenated hydrocarbon).

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

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

The method for applying the coating liquid is not particularly limited as long as the coating liquid can be applied uniformly. Examples of the coating method include a dip coating method, a spray coating method, a spin coating method and a bar coating method.

The method for removing at least a part of the solvent contained in the coating liquid is not particularly limited as long as it can evaporate the solvent in the coating liquid. Examples of the removing method include heating, depressurization, or a combination of heating and depressurization. More specifically, a method of heat treatment (hot air drying) using a high temperature dryer or a vacuum dryer can be mentioned. The temperature of the heat treatment 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.

The method for producing the photoconductor may further include at least one step of forming an intermediate layer and a step of forming a protective layer, if necessary. A known method can be appropriately selected for each of the step of forming the intermediate layer and the step of forming the protective layer.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the scope of the examples.

The following charge generators, hole transporting agents, binder resins and electron transporting agents were prepared as materials for forming the photosensitive layer of the photoconductor.

(Charge generator)
As a charge generator, Y-type titanyl phthalocyanine represented by the chemical formula (CGM-2) described in the embodiment was prepared.

(Electronic transport agent)
As the electron transporting agent, the compound (20-E1), the compound (20-E2), the compound (21-E3), the compound (22-E4), the compound (23-E5) and the compound (24-E6) described in the embodiment ) Was prepared.

(Hole transport agent)
As the hole transporting agent, the compounds (1-1) to (1-3) described in the embodiment were prepared.

Further, as the hole transporting agent used in the comparative example, the compounds represented by the chemical formulas (HTM-4) to (HTM-10) (hereinafter, each of them is described as compounds (HTM-4) to (HTM-10)). I also prepared. The compound (HTM-9) corresponds to the terphenyldiamine represented by the chemical formula (II) described in Patent Document 1.

(Binder resin)
As the binder resin, each of the resins (R-1) to (R-8) described in the embodiment was prepared.

(Resin (R-1))
The resin (R-1) was a polyarylate resin having only repeating units (10-1), (11-X1) and (11-X3) as repeating units. The resin (R-1) had two types of repeating units (11-X1) and (11-X3) as repeating units (11), and the ratio p was 0.50. The viscosity average molecular weight of the resin (R-1) was 50,500.

The resin (R-1) was synthesized by the following method. Specifically, as a reaction vessel, a three-necked flask having a capacity of 1 L equipped with a thermometer, a three-way cock, and a dropping funnel having a capacity of 200 mL was used. In a reaction vessel, 10 g (41.28 mmol) of compound (BP-10-1), 0.062 g (0.413 mmol) of tert-butylphenol, 3.92 g (98 mmol) of sodium hydroxide, and benzyltributylammonium 0.120 g (0.384 mmol) of chloride was added. The air in the reaction vessel was replaced with argon gas. 300 mL of water was added to the contents of the reaction vessel. The contents of the reaction vessel were stirred at 50 ° 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. to obtain an alkaline aqueous solution A.

On the other hand, 4.10 g (16.2 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (dichloroform of compound (DC-11-X1)) and 4,4'-oxybis benzoic acid dichloride (compound (DC-11-X3)). ) Dichloride) 4.78 g (16.2 mmol) was dissolved in 150 mL of chloroform. As a result, chloroform solution B was obtained.

Chloroform solution B was slowly added dropwise to the alkaline aqueous solution A over 110 minutes from the dropping funnel. While adjusting the temperature (liquid temperature) of the contents of the reaction vessel to 15 ± 5 ° C., the contents of the reaction vessel were stirred for 4 hours to proceed with the polymerization reaction. Then, the upper layer (aqueous layer) in the contents of the reaction vessel was removed using a decant to obtain an organic layer. Next, 400 mL of ion-exchanged water was placed in an Erlenmeyer flask having a capacity of 1 L. The obtained organic layer was added to the contents of the flask. 400 mL of chloroform and 2 mL of acetic acid were further added to the contents of the flask. The flask contents were then stirred at room temperature (25 ° C.) for 30 minutes. Then, the upper layer (aqueous layer) in the flask contents was removed using a decant to obtain an organic layer. The obtained organic layer was washed with 1 L of ion-exchanged water using a separating funnel. Washing with ion-exchanged water was repeated 5 times to obtain an organic layer washed with water.

Next, the organic layer washed with water was filtered to obtain a filtrate. 1 L of methanol was placed in a beaker with a capacity of 1 L. The obtained filtrate was slowly added dropwise to methanol in a beaker to obtain a precipitate. The precipitate was removed by filtration. The removed precipitate was vacuum dried at a temperature of 70 ° C. for 12 hours. As a result, a resin (R-1) was obtained.

(Resin (R-2))
The resin (R-2) was a polyarylate resin having only the repeating units (10-2), (11-X1) and (11-X3) as the repeating units. The resin (R-2) had two types of repeating units (11-X1) and (11-X3) as repeating units (11), and the ratio p was 0.50. The viscosity average molecular weight of the resin (R-2) was 47,500.

The resin (R-2) was synthesized by the following method. Specifically, the same method as the method for synthesizing the resin (R-1) except that the 41.28 mmol compound (BP-10-1) was changed to the 41.28 mmol compound (BP-10-2). A resin (R-2) was obtained.

(Resin (R-3))
The resin (R-3) was a polyarylate resin having only the repeating units (10-2), (11-X1) and (11-X2) as the repeating units. The resin (R-3) had two types of repeating units (11-X1) and (11-X2) as repeating units (11), and the ratio p was 0.50. The viscosity average molecular weight of the resin (R-3) was 50,500.

The resin (R-3) was synthesized by the following method. Specifically, the 41.28 mmol compound (BP-10-1) was changed to a 41.28 mmol compound (BP-10-2), and the 16.2 mmol compound (DC-11-X3). The resin (R-3) was obtained by the same method as the method for synthesizing the resin (R-1), except that the dichloride of) was changed to the dichloride of the compound (DC-11-X2) of 16.2 mmol.

(Resin (R-8))
The resin (R-8) was a polyarylate resin having only repeating units (10-4) and (11-X3) as repeating units. The viscosity average molecular weight of the resin (R-8) was 50,900.

The resin (R-8) was synthesized by the following method. Specifically, the 41.28 mmol compound (BP-10-1) was changed to a 41.28 mmol compound (BP-10-4), and the 16.2 mmol compound (DC-11-X1). ) And the dichloride of the 16.2 mmol compound (DC-11-X3) were changed to the dichloride of the 32.4 mmol compound (DC-11-X3) of the resin (R-1). A resin (R-8) was obtained by the same method as the synthesis method.

(Resin (R-4))
The resin (R-4) was a polyarylate resin having only the repeating units (10-3), (11-X1) and (11-X3) as the repeating units. The resin (R-4) had two types of repeating units (11-X1) and (11-X3) as repeating units (11), and the ratio p was 0.50. The viscosity average molecular weight of the resin (R-4) was 55,000.

The resin (R-4) was synthesized by the following method. Specifically, as a reaction vessel, a three-necked flask having a capacity of 2 L equipped with a thermometer, a three-way cock, and a dropping funnel having a capacity of 400 mL was used. In a reaction vessel, 29.10 g (82.56 mmol) of compound (BP-10-3), 0.124 g (0.826 mmol) of tert-butylphenol, 7.84 g (196 mmol) of sodium hydroxide, and benzyl 0.240 g (0.768 mmol) of tributylammonium chloride was added. The air in the reaction vessel was replaced with argon gas. 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. to obtain an alkaline aqueous solution C.

On the other hand, 9.84 g (38.9 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (dichloride of compound (DC-11-X1)) and 4,4'-oxybis benzoic acid dichloride (compound (DC-11-X3)). ) Dichloride) 11.47 g (38.9 mmol) was dissolved in 300 mL of chloroform. As a result, a chloroform solution D was obtained.

Chloroform solution D was slowly added dropwise to the alkaline aqueous solution C over 110 minutes from the dropping funnel. 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 proceed with the polymerization reaction. Then, the upper layer (aqueous layer) in the contents of the reaction vessel was removed using a decant to obtain an organic layer. Next, 500 mL of ion-exchanged water was placed in an Erlenmeyer flask having a capacity of 2 L. The obtained organic layer was added to the contents of the flask. 300 mL of chloroform and 6 mL of acetic acid were further added to the contents of the flask. The flask contents were then stirred at room temperature (25 ° C.) for 30 minutes. Then, the upper layer (aqueous layer) in the flask contents was removed using a decant to obtain an organic layer. The obtained organic layer was washed with 500 mL of ion-exchanged water using a separating funnel. Washing with ion-exchanged water was repeated 5 times to obtain an organic layer washed with water.

Next, the organic layer washed with water was filtered to obtain a filtrate. 1.5 L of methanol was placed in a beaker with a capacity of 3 L. The obtained filtrate was slowly added dropwise to methanol in a beaker to obtain a precipitate. The precipitate was removed by filtration. The removed precipitate was vacuum dried at a temperature of 70 ° C. for 12 hours. As a result, a resin (R-4) was obtained.

(Resin (R-5))
The resin (R-5) was a polycarbonate resin having only a repeating unit (R-5) as a repeating unit. The viscosity average molecular weight of the resin (R-5) was 50,600.

(Resin (R-6))
The resin (R-6) was a polycarbonate resin having only a repeating unit (R-6) as a repeating unit. The viscosity average molecular weight of the resin (R-6) was 49,400.

(Resin (R-7))
The resin (R-7) was a polycarbonate resin having only a repeating unit (R-7) as a repeating unit. The viscosity average molecular weight of the resin (R-7) was 50,900.

Next, ¹ H-NMR spectra of the synthesized resins (R-1) to (R-4) and (R-8) were measured using a proton nuclear magnetic resonance spectrometer (manufactured by JASCO Corporation, 300 MHz). did. CDCl ₃ was used as the solvent. Tetramethylsilane (TMS) was used as the internal standard sample. As typical examples of the resins (R-1) to (R-4) and (R-8), the chemical shift values of the resins (R-1) and (R-4) are shown below. From the chemical shift values, it was confirmed that the resins (R-1) and (R-4) were obtained, respectively. Regarding the resins (R-2), (R-3) and (R-8), the same method was used to obtain the resins (R-2), (R-3) and (R-8), respectively. confirmed.

Resin (R-1): ^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ = 8.85 (s, 2H), 8.29 (d, 2H), 8.23 (dd, 4H), 8.12 ( d, 2H), 7.04-7.24 (m, 16H), 2.16 (q, 4H), 1.65 (s, 6H), 0.78 (t, 6H).
Resin (R-4): ^{1 1} H-NMR (300 MHz, CDCl ₃ ) δ = 8.84 (s, 2H), 8.28 (d, 2H), 8.22 (d, 4H), 8.11 ( d, 2H), 7.10-7.31 (m, 20H), 2.12 (brs, 8H), 1.38 (brs, 28H), 1.00 (brs, 8H).

<Manufacturing of photoconductor>
Photoreceptors (A-1) to (A-20) and (B-1) to (B-8) were produced using the above-mentioned charge generator, hole transport agent, binder resin, and electron transport agent.

(Manufacturing of photoconductor (A-1))
In the container, 2.0 parts by mass of Y-type titanyl phthalocyanine as a charge generator, 60.0 parts by mass of compound (1-1) as a hole transport agent, and 100.0 parts of resin (R-1) as a binder resin. A parts by mass, 25.0 parts by mass of the compound (20-E1) as an electron transporting agent, and 800.0 parts by mass of tetrahydrofuran as a solvent were added. The contents of the container were mixed using a ball mill for 50 hours to disperse the material in a solvent. As a result, a coating liquid was obtained. The coating liquid was applied onto a conductive substrate (aluminum drum-shaped support, diameter 30 mm, total length 238.5 mm) by a dip coating method. The applied coating liquid was dried with hot air at 120 ° C. for 60 minutes. As a result, a single photosensitive layer (thickness 28 μm) was formed on the conductive substrate. As a result, a photoconductor (A-1) was obtained. In the photoconductor (A-1), a single-layer photosensitive layer was provided on the conductive substrate.

(Manufacture of Photoreceptors (A-2) to (A-20) and (B-1) to (B-8))
Each of the photoconductors (A-2) to (A-20) and (B-1) to (B-8) is produced in the same manner as in the production of the photoconductor (A-1) except that the following points are changed. Manufactured. In the production of the photoconductor (A-1), 60.0 parts by mass of the compound (1-1) was used as the hole transporting agent, but the photoconductors (A-2) to (A-20) and (B-1) were used. )-(B-8), the hole transporting agents of the types and amounts shown in Tables 1 to 3 were used. Although the resin (R-1) was used as the binder resin in the production of the photoconductor (A-1), the photoconductors (A-2) to (A-20) and (B-1) to (B-8) In each production of, the binder resins of the types shown in Tables 1 to 3 were used. In the production of the photoconductor (A-1), 25.0 parts by mass of the compound (20-E1) was used as the electron transporting agent, but the photoconductors (A-2) to (A-20) and (B-1) were used. In each production of (B-8), the types and amounts of electron transporting agents shown in Tables 1 to 3 were used.

<Evaluation of charging characteristics of photoconductor>
The charging characteristics of each of the photoconductors (A-1) to (A-20) and (B-1) to (B-8) were evaluated in an environment of a temperature of 10 ° C. and a relative humidity of 20% RH. .. Specifically, a drum sensitivity tester (manufactured by Gentec Co., Ltd.) was used to charge the photoconductor under the conditions of a rotation speed of the photoconductor of 31 rpm and a current flowing into the photoconductor + 8 μA. The surface potential of the charged photoconductor was measured. The measured surface potential was defined as the charging potential (V ₀ , unit: + V) of the photoconductor. The charging potential (V ₀ ) of the photoconductor is shown in Tables 1 to 3.

<Evaluation of sensitivity characteristics of photoconductor>
The sensitivity characteristics of each of the photoconductors (A-1) to (A-20) and (B-1) to (B-8) were evaluated in an environment of a temperature of 10 ° C. and a relative humidity of 20% RH. .. Specifically, the surface of the photoconductor was charged to + 620 V using a drum sensitivity tester (manufactured by Gentec Co., Ltd.). Next, monochromatic light (wavelength: 780 nm, exposure amount: 1.3 μJ / cm ² ) was taken out from the light of the halogen lamp using a bandpass filter and irradiated to the surface of the photoconductor. The surface potential of the photoconductor was measured when 80 milliseconds had elapsed from the end of irradiation with monochromatic light. The measured surface potential was defined as the post-exposure potential ( _VL , unit: + V) of the photoconductor. The post-exposure potential ( _VL ) of the photoconductor is shown in Tables 1 to 3. The smaller the absolute value of the post-exposure potential ( _VL ), the better the sensitivity characteristics of the photoconductor. Photoreceptors having an absolute value of post-exposure potential ( _VL ) of 110 V or more were evaluated as having poor sensitivity characteristics (indicated by x in Table 3).

<Evaluation of crystallization suppression of photoconductor>
The entire surface (photosensitive layer) of each of the photoconductors (A-1) to (A-20) and (B-1) to (B-8) was observed with the naked eye. Then, the presence or absence of a crystallized portion in the photosensitive layer was confirmed. Based on the confirmation results, it was evaluated whether or not crystallization was suppressed by the following evaluation criteria. The evaluation results are shown in Tables 1 to 3. The photoconductor having an evaluation of C was evaluated as not suppressing the crystallization of the photosensitive layer (indicated by x in Table 3).

(Evaluation criteria for crystallization suppression)
Evaluation A: No crystallized part was confirmed.
Evaluation B: A few crystallized parts were confirmed.
Evaluation C: The crystallized part was clearly confirmed.

In Tables 1 to 3, HTM, Resin, ETM, parts, V ₀ and _VL indicate hole transporting agent, binder resin, electron transporting agent, mass parts, charging potential and post-exposure potential, respectively.

In Tables 1 to 3, "HTM / Resin" indicates the ratio of the mass m _HTM of the hole transporting agent to the mass m _Resin of the binder resin m _HTM / m _Resin . The ratio m _HTM / m _Resin was calculated from the calculation formula “ratio m _HTM / m _Resin = amount of hole transporting agent (unit: parts by mass) / amount of binder resin (unit: parts by mass)”.

In Tables 1 to 3, "ETM / HTM" indicates the ratio of the mass m _ETM of the electron transporting agent to the mass m _HTM of the hole transporting agent m _ETM / m _HTM . The ratio m _ETM / m _HTM was calculated from the formula “ratio m _ETM / m _HTM = amount of electron transporting agent (unit: parts by mass) / amount of hole transporting agent (unit: parts by mass)”.

Each of the photoconductors (A-1) to (A-20) provided a conductive substrate and a photosensitive layer. The photosensitive layer was a single layer. The photosensitive layer contained a charge generator, a hole transport agent, a binder resin, and an electron transport agent. The ratio of the mass of the hole transporting agent to the mass of the binder resin was 0.50 or more. The hole transport agent contained compound (1). Specifically, in each of the photoconductors (A-1) to (A-20), the compound (1-1), (1-2) or the compound (1-2) included in the general formula (1) is used as a hole transporting agent. (1-3) was contained in the photosensitive layer. Therefore, as is clear from Tables 1 and 2, in the photoconductors (A-1) to (A-20), the absolute value of the post-exposure potential ( _VL ) is less than 110 V, and the electrical characteristics (particularly the sensitivity characteristics). ) Was excellent. Further, the evaluation of the suppression of crystallization of the photoconductors (A-1) to (A-20) was A or B, and the crystallization of the photosensitive layer was suppressed.

On the other hand, in each of the photoconductors (B-1) to (B-7), the photosensitive layer contained any of the compounds (HTM-4) to (HTM-10) as a hole transporting agent. However, none of the compounds (HTM-4) to (HTM-10) was included in the general formula (1). Therefore, as is clear from Table 3, in the photoconductors (B-1) to (B-7), the absolute value of the post-exposure potential ( _VL ) is 110 V or more, and the electrical characteristics (particularly the sensitivity characteristics) are inferior. Was there. Further, the evaluation of the suppression of crystallization of the photoconductors (B-1) to (B-4) was C, and the crystallization of the photosensitive layer was not suppressed.

In the photoconductor (B-8), the ratio of the mass of the hole transporting agent to the mass of the binder resin was less than 0.50. Therefore, as is clear from Table 3, in the photoconductor (B-8), the absolute value of the post-exposure potential ( _VL ) was 110 V or more, and the electrical characteristics (particularly the sensitivity characteristics) were inferior.

From the above, it was shown that the photoconductor according to the present invention can improve the electrical characteristics and suppress the crystallization of the photosensitive layer.

The compound according to the present invention can be used for a photoconductor. The photoconductor according to the present invention can be used in an image forming apparatus.

1 Electrophotographic photosensitive member 2 Conductive substrate 3 Photosensitive layer 4 Intermediate layer 5 Protective layer

Claims (5)

An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer.
The photosensitive layer is a single layer and
The photosensitive layer contains a charge generator, a hole transport agent, a binder resin, and an electron transport agent.
The ratio of the mass of the hole transporting agent to the mass of the binder resin is 0.50 or more.
The hole transporting agent is an electrophotographic photosensitive member containing a compound represented by the chemical formula (1-3) .

The electrophotographic photosensitive member according to claim 1, wherein the ratio of the mass of the electron transporting agent to the mass of the hole transporting agent is 0.01 or more and 1.50 or less. The binder resin contains a polyarylate resin and contains.
The polyarylate resin according to claim 1 or 2 , wherein the polyarylate resin contains at least one of the repeating units represented by the general formula (10) and at least one of the repeating units represented by the general formula (11). Electrophotographic photosensitive member.

(In the general formula (10),
R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group.
R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, or R ¹³ and R ¹⁴ are bonded to each other and have carbon atoms. Represents a cycloalkylidene group of 5 or more and 14 or less,
When one type of repeating unit represented by the general formula (11) is included, in the general formula (11), X represents a divalent group represented by the chemical formula (X1).
When at least two types of repeating units represented by the general formula (11) are included, X in the general formula (11) of at least one of the two types is represented by the chemical formula (X1). Represents a valence group, where X in the general formula (11) of another species is divalent represented by chemical formula (X2), chemical formula (X3), chemical formula (X4), chemical formula (X5) or chemical formula (X6). Represents the basis of. )

The binder resin contains a polyarylate resin and contains.
The polyarylate resin is a polyarylate resin containing a repeating unit represented by the chemical formula (10-1), the chemical formula (11-X1) and the chemical formula (11-X3).

A polyarylate resin containing a repeating unit represented by the chemical formula (10-2), the chemical formula (11-X1) and the chemical formula (11-X3).

A polyarylate resin containing a repeating unit represented by the chemical formula (10-2), the chemical formula (11-X1) and the chemical formula (11-X2), or

The electron according to any one of claims 1 to 3 , which is a polyarylate resin containing a repeating unit represented by the chemical formula (10-3), the chemical formula (11-X1) and the chemical formula (11-X3). Photophotoreceptor.

The binder resin contains a polycarbonate resin and contains
The electrophotographic photosensitive member according to claim 1 or 2 , wherein the polycarbonate resin contains a repeating unit represented by the chemical formula (R-5) or the chemical formula (R-6).

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