JP2017114807A - Triarylamine hydrazone compound and electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound that improves the electric characteristics of electrophotographic photoreceptors.SOLUTION: A triarylamine hydrazone compound is represented by formula (1) (R-Rindependently represent halogen, a substituted/unsubstituted C1-6 alkyl group, a C1-6 alkoxy group or a substituted/unsubstituted C6-14 aryl group; a is an integer of 1 to 3 or less; b and c independently represent 0 or 1; d, e, f, g, h and i independently represent an integer of 0-5).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a compound (particularly a triarylamine hydrazone compound) and an electrophotographic photoreceptor.

  The electrophotographic photosensitive member is used in an electrophotographic image forming apparatus. The electrophotographic photoreceptor includes a photosensitive layer. As the electrophotographic photosensitive member, for example, a multilayer electrophotographic photosensitive member or a single layer type electrophotographic photosensitive member is used. The multilayer electrophotographic photoreceptor includes, as a photosensitive layer, a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. The single layer type electrophotographic photosensitive member includes a single layer type photosensitive layer having a charge generation function and a charge transport function as a photosensitive layer.

  The electrophotographic photosensitive member described in Patent Document 1 includes a photosensitive layer. The photosensitive layer contains, for example, a compound represented by the chemical formula (HA) or (H-B).

JP 2006-008670 A

  However, the electrophotographic photosensitive member described in Patent Document 1 has insufficient electrical characteristics.

  The present invention has been made in view of the above problems, and an object thereof is to provide a compound that improves the electrical characteristics of an electrophotographic photoreceptor. Another object of the present invention is to provide an electrophotographic photoreceptor excellent in electrical characteristics by containing such a compound.

  The compound of the present invention is represented by the following general formula (1).

In the general formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a halogen atom or a carbon atom number of 1 to 6 that may have a substituent. And an alkyl group having 1 to 6 carbon atoms which may have a substituent or an aryl group having 6 to 14 carbon atoms which may have a substituent. a represents an integer of 1 to 3. b and c each independently represents 0 or 1; d, e, f, g, h and i each independently represents an integer of 0 or more and 5 or less. When d represents an integer of 2 or more and 5 or less, the plurality of R ₁ may be the same or different. When e represents an integer of 2 or more and 5 or less, the plurality of R ₂ may be the same or different. When f represents an integer of 2 to 5, a plurality of R ₃ may be the same or different. When g represents an integer of 2 to 5, a plurality of R ₄ may be the same or different. When h represents an integer of 2 to 5, a plurality of R ₅ may be the same or different. When i represents an integer of 2 or more and 5 or less, the plurality of R ₆ may be the same or different.

  The electrophotographic photoreceptor of the present invention includes a photosensitive layer. The photosensitive layer contains the compound described above.

  According to the compound of the present invention, the electrical characteristics of the electrophotographic photoreceptor can be improved. Moreover, according to the electrophotographic photosensitive member of the present invention, the electrical characteristics can be improved by containing such a compound.

It is a < ¹ > H-NMR spectrum of a compound denoted by a chemical formula (H-2) concerning a first embodiment of the present invention. ¹ is a ¹ H-NMR spectrum of a compound represented by a chemical formula (H-4) according to a first embodiment of the present invention. (A), (b) and (c) are schematic sectional views showing examples of the electrophotographic photosensitive member according to the second embodiment of the present invention, respectively. (A), (b) and (c) is a schematic sectional drawing which shows another example of the electrophotographic photoreceptor which concerns on 2nd embodiment of this 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 implemented with appropriate modifications within the scope of the object of the present invention. In addition, about the location where description overlaps, although description may be abbreviate | omitted suitably, the summary of invention is not limited.

  Hereinafter, a compound and its derivatives may be generically named by adding “system” after the compound name. In addition, when “polymer” is added after the compound name to indicate the polymer name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof. Furthermore, the reactions represented by the reaction formulas (R-1) to (R-19) may be described as reactions (R-1) to (R-19), respectively. Compounds represented by the general formulas (1) to (7), (6-1), (6-2) and (6-3) are respectively represented by the compounds (1) to (7), (6-1), Sometimes described as (6-2) and (6-3). Chemical formulas (2a), (3a), (4a), (5a), (6a) to (6c), (7a), (8), (10a), (10b), (11a), (12a), ( 12b), (13a) to (13e) and (14a) to (14e) are represented by compounds (2a), (3a), (4a), (5a), (6a) to (6c), respectively. , (7a), (8), (10a), (10b), (11a), (12a), (12b), (13a) to (13e), and (14a) to (14e). .

  Hereinafter, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms have the following meanings unless otherwise specified: It is.

  The halogen atom is, for example, fluorine (fluoro group), chlorine (chloro group) or bromine (bromo group).

  The alkyl group having 1 to 6 carbon atoms is a linear or branched alkyl group having 1 to 6 carbon atoms that is unsubstituted. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, and neopentyl group. Or a hexyl group is mentioned.

  The alkoxy group having 1 to 6 carbon atoms is a linear or branched alkoxy group having 1 to 6 carbon atoms which is unsubstituted. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, t-butoxy, pentyloxy, iso A pentyloxy group, a neopentyloxy group, or a hexyloxy group may be mentioned.

  Examples of the aryl group having 6 to 14 carbon atoms include an unsubstituted aromatic monocyclic hydrocarbon group having 6 to 14 carbon atoms and an unsubstituted aromatic condensed bicyclic carbon group having 6 to 14 carbon atoms. A hydrogen group or an unsubstituted aromatic condensed tricyclic hydrocarbon group having 6 to 14 elemental atoms. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

<First embodiment: Compound (1)>
1st embodiment of this invention is a compound (1). Compound (1) is a triarylamine hydrazone compound, that is, a hydrazone compound containing a triarylamine structure. The compound (1) is represented by the following general formula (1).

In general formula (1), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a halogen atom or a carbon atom having 1 to 6 carbon atoms which may have a substituent. It represents an alkyl group, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having 6 to 14 carbon atoms which may have a substituent. a represents an integer of 1 to 3. b and c each independently represents 0 or 1; d, e, f, g, h and i each independently represents an integer of 0 or more and 5 or less. When d represents an integer of 2 or more and 5 or less, the plurality of R ₁ may be the same or different. When e represents an integer of 2 or more and 5 or less, the plurality of R ₂ may be the same or different. When f represents an integer of 2 to 5, a plurality of R ₃ may be the same or different. When g represents an integer of 2 to 5, a plurality of R ₄ may be the same or different. When h represents an integer of 2 to 5, a plurality of R ₅ may be the same or different. When i represents an integer of 2 or more and 5 or less, the plurality of R ₆ may be the same or different.

  Compound (1) can improve the electrical characteristics of an electrophotographic photoreceptor (hereinafter sometimes referred to as a photoreceptor). The reason is presumed as follows.

  First, compound (1) has two triphenylamine moieties. There are 1 to 3 conjugated bonds (corresponding to a in the general formula (1)) between two triphenylamine sites. Therefore, the molecular structure of compound (1) becomes moderately large. This tends to reduce the distance (hopping distance) between the π electron cloud of one compound (1) and the π electron cloud of the other compound (1) present in the photosensitive layer. As a result, it is considered that the hole mobility between the compounds (1) is improved, and the electrical characteristics of the photoreceptor are improved.

  Secondly, the compound (1) has two groups represented by the chemical formula “—CH═N—N═”. The group represented by the chemical formula “—CH═N—N═” is a polar group. Therefore, compound (1) is easily dissolved in a solvent for forming the photosensitive layer. Moreover, when binder resin has a polar group (for example, carbonyl group), it is thought that compatibility with the compound (1) which has a polar group, and binder resin improves. This makes it easier to obtain a photosensitive layer in which compound (1) is uniformly dispersed. As a result, it is considered that the electrical characteristics of the photoreceptor are improved.

  Thirdly, the compound (1) has a structure that easily overlaps with the charge generating agent having a planar structure. When the area where the compound (1) and the charge generator overlap is increased, holes tend to be efficiently transferred from the charge generator to the compound (1). As a result, it is considered that the electrical characteristics of the photoreceptor are improved.

The alkyl group having 1 to 6 carbon atoms represented by R _{1 to} R ₆ in the general formula (1) is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group having 1 to 6 carbon atoms represented by R _{1 to} R ₆ may have a substituent. Examples of the substituent of the alkyl group having 1 to 6 carbon atoms include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms. The number of substituents is not particularly limited, but is preferably 3 or less.

The alkoxy group having 1 to 6 carbon atoms represented by R _{1 to} R ₆ in the general formula (1) is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. The alkoxy group having 1 to 6 carbon atoms represented by R _{1 to} R ₆ may have a substituent. Examples of the substituent of the alkoxy group having 1 to 6 carbon atoms include a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an aryl group having 6 to 14 carbon atoms. The number of substituents is not particularly limited, but is preferably 3 or less.

The aryl group having 6 to 14 carbon atoms represented by R _{1 to} R ₆ in the general formula (1) is an aromatic monocyclic hydrocarbon group having 6 to 14 carbon atoms or 6 to 14 carbon atoms. The following aromatic condensed bicyclic hydrocarbon groups are preferable, and a phenyl group is more preferable. The aryl group having 6 to 14 carbon atoms represented by R _{1 to} R ₆ may have a substituent. Examples of the substituent of the aryl group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 6 to 14 carbon atoms. An aryl group is mentioned. The number of substituents is not particularly limited, but is preferably 3 or less.

In order to improve the electrical characteristics of the photoreceptor, R _{1 to} R ₆ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 carbon atoms. It is preferable to represent an aryl group of 14 or less.

  In general formula (1), a preferably represents 2 or 3. When a is 2 or 3, the molecular structure of the compound (1) becomes moderately large, and the π electron cloud of one compound (1) and the π electron cloud of the other compound (1) existing in the photosensitive layer Tends to be smaller (hopping distance). As a result, it is considered that the hole mobility between the compounds (1) is improved, and the electrical characteristics of the photoreceptor are improved.

  In order to improve the electrical characteristics of the photoreceptor, it is preferable that d, e, f, g, h and i in the general formula (1) each independently represent an integer of 0 or more and 2 or less. For the same reason, it is more preferable that d and g each independently represent 1 or 2. For the same reason, it is more preferable that e, f, h and i each represent 0.

When d, e, f, g, h or i represents an integer of 2 or more and 5 or less, a plurality of corresponding R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different. Good. For example, when d represents 2, two R _{1 s} may be the same as or different from each other. For example, when d represents 2, two R _{1 s} may each be a methyl group, or one of the two R _{1 s} may be a methyl group and the other may be a methoxy group.

When d, e, f, g, h or i represents an integer of 1 or more and 5 or less, the corresponding substitution positions of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are not particularly limited. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is a para position, a meta position or an ortho position of the phenyl group to which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is bonded. Any of these may be combined. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is preferably bonded to the ortho position and / or the para position of the phenyl group.

  In general formula (1), the group represented by the following general formula (1-1) is preferably the same as the group represented by the following general formula (1-2). This is because the compound (1) can be efficiently produced while reducing the number of reaction steps while maintaining the electrical characteristics of the photoreceptor.

In the general formula _{(1-1), R 1, R} 2, R 3, b, d, e and f are, R ₁ in the formula _{(1), R 2, R 3, b} , d, e and f It is synonymous with. R ₁ in the general formula (1-1) _{in, R 2, R 3, b} , preferred examples of d, e and f are, R ₁ in the general formula (1) _{in, R 2, R 3, b} , d , E and f are the same as the preferred examples. Y ₁ represents a binding site.

In the general formula _{(1-2), R 4, R} 5, R 6, c, g, h and i are, in general formula (1) _{R 4, R 5, R 6} , c, g, h and i It is synonymous with. Formula (1-2) in _{R 4, R 5, R 6} , c, g , suitable examples of h and i are, in general formula (1) _{R 4, R 5, R 6} , c, g , H and i are the same as the preferred examples. Y ₂ represents a binding site.

Y ₁ of the group represented by the general formula (1-1) is bonded to Y _{1 of the} group represented by the following general formula (1-3). A single bond is formed between the nitrogen atom to which Y ₁ in General Formula (1-1) is bonded and the carbon atom to which Y ₁ in General Formula (1-3) is bonded. The group represented by the general formula (1-2) Y ₂ binds to Y ₂ of the group represented by the general formula (1-3). A single bond is formed between the nitrogen atom to which Y ₂ in General Formula (1-2) is bonded and the carbon atom to which Y ₂ in General Formula (1-3) is bonded.

In general formula (1-3), a is synonymous with a in general formula (1). The suitable example of a in General formula (1-3) is the same as the suitable example of a in General formula (1). Y ₁ and Y ₂ each represent a binding site.

When the group represented by the general formula (1-1) is the same as the group represented by the general formula (1-2), R _{1 to} R ₆ and b to i in the general formula (1) are as follows: Have a relationship. In general formula (1), R ₁ and R ₄ represent the same group. R ₂ and R ₅ represent the same group. R ₃ and R ₆ represent the same group. b and c represent the same integer. d and g represent the same integer. e and h represent the same integer. f and i represent the same integer. When d and g represent the same integer of 2 or more and 5 or less, a plurality of R ₁ may be the same or different, and a plurality of R ₄ may be the same or different. In this case, R ₁ bonded to one bonding position of one phenyl group and R ₄ bonded to the substitution position corresponding to R ₁ of another phenyl group are the same. An example will be described to facilitate understanding. For example, the R ₁ that bind to the para position of one phenyl group may be the same or different than the R ₁ that bind to the ortho position. In this case, the R ₄ which binds at the para-position of another phenyl group may be the same or different and R ₄ is bonded to the ortho position. In this case, R ₁ bonded to the para position of one phenyl group and R ₄ bonded to the para position of another phenyl group are the same. R ₁ bonded to the ortho position of one phenyl group and R ₄ bonded to the ortho position of another phenyl group are the same. Even when e and h each represent the same integer of 2 to 5, the plurality of R ₂ and the plurality of R ₅ have the same relationship. When f and i represent the same integer of 2 or more and 5 or less, the plurality of R ₃ and the plurality of R ₆ have the same relationship.

When the group represented by the general formula (1-1) is the same as the group represented by the general formula (1-2), R ₂ , R ₃ , R ₅ and R ₆ in the general formula (1) are It is preferable that each represents the same group, and e, f, h and i each represent the same integer.

Specific examples of the compound (1) include compounds represented by the following chemical formulas (H-1), (H-2), (H-3), (H-4) or (H-5) (hereinafter referred to as compounds). (H-1), (H-2), (H-3), (H-4) or (H-5) may be mentioned). As representative examples, ¹ H-NMR spectra of the compounds (H-2) and (H-4) are shown in FIGS.

[Production Method of Compound (1)]
Compound (1) is produced, for example, according to the following reactions (R-1) to (R-10) or by a method analogous thereto. In addition to these reactions, appropriate steps may be included as necessary. In reaction (R-1) ~ indicated by (R-10) Reaction Scheme, R ₁ to R ₆ and a~i the general formula (1) in the same meanings as R ₁ to R ₆ and a~i of. X represents a halogen atom.

[Production of Compound (6)]
First, a compound (6) is manufactured. Compound (6) is represented by the following general formula (6). Compound (6) is a raw material for producing compound (1). As a manufacturing method of compound (6), the manufacturing method of compounds (6-1), (6-2), and (6-3) will be described as an example. Compounds (6-1), (6-2), and (6-3) are compounds in which a in formula (6) is 1, 2, and 3, respectively.

  Compound (6-1) is produced according to the following reactions (R-1) and (R-2). Compound (6-2) is produced according to the following reactions (R-1) and (R-3).

  In the reaction (R-1), 1 molar equivalent of the compound (3) is obtained by reacting 1 molar equivalent of the compound (2) with 1 molar equivalent of triethyl phosphite. In reaction (R-1), it is preferable to add 1 to 2.5 mol of triethyl phosphite with respect to 1 mol of compound (2). The reaction temperature for reaction (R-1) is preferably 160 ° C. or higher and 200 ° C. or lower. The reaction time for reaction (R-1) is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction (R-2), 1 molar equivalent of the compound (3) and 1 molar equivalent of the compound (4) are reacted to obtain 1 molar equivalent of the compound (6-1). Reaction (R-2) is a Wittig reaction. In reaction (R-2), it is preferable to add 1 mol or more and 5 mol or less of compound (4) with respect to 1 mol of compound (3). The reaction temperature for reaction (R-2) is preferably 0 ° C. or higher and 50 ° C. or lower. The reaction time for reaction (R-2) is preferably 2 hours or longer and 24 hours or shorter.

  Reaction (R-2) may be performed in the presence of a base. Examples of the base include sodium alkoxide (specifically sodium methoxide or sodium ethoxide), metal hydride (specifically sodium hydride or potassium hydride) or metal salt (specifically n -Butyllithium). These bases may be used individually by 1 type, and may be used in combination of 2 or more type. The amount of the base added is preferably 1 mol or more and 2 mol or less with respect to 1 mol of the compound (3).

  Reaction (R-2) may be performed in a solvent. Examples of the solvent include ethers (specifically, tetrahydrofuran, diethyl ether or dioxane), halogenated hydrocarbons (specifically, methylene chloride, chloroform or dichloroethane) or aromatic hydrocarbons (specifically, Benzene or toluene).

  In the reaction (R-3), 1 molar equivalent of the compound (3) and 1 molar equivalent of the compound (5) are reacted to obtain 1 molar equivalent of the compound (6-2). Reaction (R-3) is a Wittig reaction. Reaction (R-3) can be carried out in the same manner as in reaction (R-2), except that compound (5) is used in place of compound (4).

  Compound (6-3) is produced according to the following reactions (R-4) and (R-5).

  In reaction (R-4), 1 molar equivalent of compound (7) is reacted with 2 molar equivalents of triethyl phosphite to give 1 molar equivalent of compound (8). In the reaction (R-4), 2 mol or more and 5 mol or less of triethyl phosphite is preferably added to 1 mol of the compound (7). The reaction temperature for reaction (R-4) is preferably 160 ° C. or higher and 200 ° C. or lower. The reaction time for reaction (R-4) is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction (R-5), 1 molar equivalent of the compound (8) and 2 molar equivalents of the compound (4) are reacted to obtain 1 molar equivalent of the compound (6-3). Reaction (R-5) is a Wittig reaction. In reaction (R-5), it is preferable to add 2 mol or more and 10 mol or less of compound (4) with respect to 1 mol of compound (8). Reaction (R-5) may be performed in the presence of a base. Reaction (R-5) may be carried out in a solvent. Examples of the base and solvent used in the reaction (R-5) are the same as those of the base and solvent used in the reaction (R-2). The reaction temperature for reaction (R-5) is preferably 0 ° C. or higher and 50 ° C. or lower. The reaction time for reaction (R-5) is preferably 2 hours or longer and 24 hours or shorter.

[Production of Compound (12)]
Next, compound (12) is produced according to the following reaction (R-6). Compound (12) is a raw material for producing compound (14).

  In the reaction (R-6), 1 molar equivalent of the compound (10) is reacted with 1 molar equivalent of the compound (11, hydrochloride of diphenylhydrazine derivative) to obtain 1 molar equivalent of the compound (12). In reaction (R-6), it is preferable to add 1 mol or more and 2.5 mol or less of compound (11) with respect to 1 mol of compound (10). The reaction temperature for reaction (R-6) is preferably from 80 ° C to 150 ° C. The reaction time for reaction (R-6) is preferably 2 hours or longer and 10 hours or shorter.

  Reaction (R-6) may be performed in the presence of a catalyst. Examples of the catalyst include an acid catalyst, and more specifically, p-toluenesulfonic acid, camphorsulfonic acid, or pyridinium-p-toluenesulfonic acid. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. The addition amount of the catalyst is a small amount with respect to 1 mol of the compound (10), and specifically, it is preferably 0.01 mol or more and 0.5 mol or less.

  Reaction (R-6) may be carried out in a solvent. The example of the solvent used by reaction (R-6) is the same as the example of the solvent used by reaction (R-2).

[Production of Compound (14)]
Next, compound (14) is produced according to the following reaction (R-7). Compound (14) is a raw material for producing compound (1).

  In the reaction (R-7), 1 molar equivalent of the compound (12) and 1 molar equivalent of the compound (13) are reacted to obtain 1 molar equivalent of the compound (14). Reaction (R-7) is a coupling reaction. In reaction (R-7), it is preferable to add 1 mol or more and 2.5 mol or less of compound (13) with respect to 1 mol of compound (12). The reaction temperature for reaction (R-7) is preferably from 80 ° C to 140 ° C. The reaction time for reaction (R-7) is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction (R-7), a palladium compound may be used as a catalyst. Examples of the palladium compound include a tetravalent palladium compound, a divalent palladium compound, and other palladium compounds. Examples of the tetravalent palladium compound include sodium hexachloropalladium (IV) tetrahydrate or potassium hexachloropalladium (IV) tetrahydrate. Examples of the divalent palladium compound include palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium acetyl acetate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (triphenylphosphine). ) Palladium (II), dichlorotetramine palladium (II) or dichloro (cycloocta-1,5-diene) palladium (II). Examples of other palladium compounds include tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), and tetrakis (triphenylphosphine) palladium (0). A palladium compound may be used individually by 1 type, and may be used in combination of 2 or more type. The addition amount of the palladium compound is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the compound (12).

  The palladium compound may have a structure including a ligand. Thereby, it becomes easy to improve the reactivity of reaction (R-7). Examples of the ligand include tricyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, trifurylphosphine, tri (o-tolyl) phosphine, dicyclohexylphenylphosphine, tri (t-butyl) phosphine, and 2,2′-bis. (Diphenylphosphino) -1,1′-binaphthyl or 2,2′-bis [(diphenylphosphino) diphenyl] ether. A ligand may be used individually by 1 type and may be used in combination of 2 or more type. The addition amount of the ligand is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the compound (12).

  Reaction (R-7) may be carried out in the presence of a base. Thereby, it is thought that catalyst activity can be improved. The base may be an inorganic base or an organic base. Examples of the organic base include alkali metal alkoxides, specifically, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide or potassium tert-butoxide. Can be mentioned. Examples of the inorganic base include tripotassium phosphate and cesium fluoride. When adding 0.0005 mol or more and 20 mol or less of the palladium compound to 1 mol of the compound (12), the amount of the base added is preferably 1 mol or more and 50 mol or less, and 1 mol or more and 30 mol or less. It is more preferable that

  Reaction (R-7) may be carried out in a solvent. Examples of the solvent include xylene (specifically, o-xylene), toluene, tetrahydrofuran, or dimethylformamide.

[Production of Compound (17)]
Next, compound (17) is produced according to the following reaction (R-8). Compound (17) is a raw material for producing compound (19).

  In the reaction (R-8), 1 molar equivalent of the compound (15) is reacted with 1 molar equivalent of the compound (16, hydrochloride of diphenylhydrazine derivative) to obtain 1 molar equivalent of the compound (17). Reaction (R-8) is similar to reaction (R-6) except that compound (15) is used instead of compound (10) and compound (16) is used instead of compound (11). A similar method can be used.

[Production of Compound (19)]
Next, according to the following reaction (R-9), a compound (19) is manufactured. Compound (19) is a raw material for producing compound (1).

  In the reaction (R-9), 1 molar equivalent of the compound (17) and 1 molar equivalent of the compound (18) are reacted to obtain 1 molar equivalent of the compound (19). Reaction (R-9) is a coupling reaction. Reaction (R-9) is similar to reaction (R-7) except that compound (17) is used instead of compound (12) and compound (18) is used instead of compound (13). A similar method can be used.

[Production of Compound (1)]
Next, according to the following reaction (R-10), the target compound (1) is produced.

  In the reaction (R-10), 1 molar equivalent of the compound (6), 1 molar equivalent of the compound (14) and 1 molar equivalent of the compound (19) are reacted to obtain 1 molar equivalent of the compound (1). . Reaction (R-10) is a coupling reaction. In reaction (R-10), 1 mol to 2.5 mol of compound (14) and 1 mol to 2.5 mol of compound (19) are added to 1 mol of compound (6). Is preferred. The reaction temperature for reaction (R-10) is preferably from 80 ° C to 140 ° C. The reaction time for reaction (R-10) is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction (R-10), a palladium compound may be used as a catalyst. The palladium compound may have a structure including a ligand. Reaction (R-10) may be carried out in the presence of a base. Reaction (R-10) may be carried out in a solvent. Examples of the catalyst, ligand, base and solvent used in the reaction (R-10) are the same as those of the catalyst, ligand, base and solvent used in the reaction (R-7).

  In addition, when manufacturing the compound (1) whose group represented by general formula (1-1) is the same as the group represented by general formula (1-2), compound (14), compound (19), Become the same compound. In this case, in the reaction (R-10), 1 molar equivalent of the compound (1) is reacted with 2 molar equivalents of the compound (14) or the compound (19) to obtain 1 molar equivalent of the compound (1). Just do it. Either the step of producing compound (14) or the step of producing compound (19) can be omitted.

  By purifying the reaction product obtained in the reaction (R-10) as necessary, the target compound (1) can be isolated. As a purification method, a known method is appropriately employed. Purification may be performed, for example, by crystallization or silica gel chromatography. As a solvent used for purification, for example, a mixed solvent of chloroform and hexane may be used.

<Second Embodiment: Photoconductor>
The second embodiment relates to a photoreceptor. The photoreceptor may be a multilayer photoreceptor or a single layer photoreceptor. The photoreceptor includes a photosensitive layer containing the compound (1) described in the first embodiment.

<1. Multilayer photoreceptor>
Hereinafter, the structure of the photoreceptor 1 when the photoreceptor 1 is a multilayer photoreceptor will be described with reference to FIG. FIG. 3 is a schematic cross-sectional view showing a stacked type photoreceptor that is an example of the photoreceptor 1 according to the present embodiment.

  As shown in FIG. 3A, the laminated photoreceptor as the photoreceptor 1 includes, for example, a conductive substrate 2 and a photosensitive layer 3. The multilayer photoreceptor includes a charge generation layer 3 a and a charge transport layer 3 b as the photosensitive layer 3.

  As shown in FIG. 3 (b), in the laminated type photoconductor as the photoconductor 1, the charge transport layer 3b is provided on the conductive substrate 2, and the charge generation layer 3a is provided on the charge transport layer 3b. Good. However, since the charge transport layer 3b is generally thicker than the charge generation layer 3a, the charge transport layer 3b is less likely to be damaged than the charge generation layer 3a. For this reason, in order to improve the wear resistance of the multilayer photoreceptor, as shown in FIG. 3A, a charge generation layer 3a is provided on the conductive substrate 2, and charge transport is performed on the charge generation layer 3a. A layer 3b is preferably provided.

  As shown in FIG. 3C, the multilayer photoreceptor as the photoreceptor 1 may include a conductive substrate 2, a photosensitive layer 3, and an intermediate layer (undercoat layer) 4. The intermediate layer 4 is provided between the conductive substrate 2 and the photosensitive layer 3. Further, a protective layer 5 (see FIG. 4) may be provided on the photosensitive layer 3.

  The thicknesses of the charge generation layer 3a and the charge transport layer 3b are not particularly limited as long as the functions as the respective layers can be sufficiently expressed. The thickness of the charge generation layer 3a 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 thickness of the charge transport layer 3b is preferably 2 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.

  The charge generation layer 3a in the photosensitive layer 3 contains a charge generation agent. The charge generation layer 3a may contain a charge generation layer binder resin (hereinafter sometimes referred to as a base resin). The charge generation layer 3a may contain various additives as necessary.

  The charge transport layer 3b in the photosensitive layer 3 contains a hole transport agent. The charge transport layer 3b may contain a binder resin. The charge transport layer 3b may contain an electron acceptor compound and various additives as necessary. The structure of the photoconductor 1 when the photoconductor 1 is a stacked type photoconductor has been described above with reference to FIG.

<2. Single-layer type photoreceptor>
Hereinafter, the structure of the photoreceptor 1 when the photoreceptor 1 is a single-layer photoreceptor will be described with reference to FIG. FIG. 4 is a schematic cross-sectional view showing a single-layer type photoreceptor that is another example of the photoreceptor 1 according to the present embodiment.

  As shown in FIG. 4A, the single layer type photoreceptor as the photoreceptor 1 includes, for example, a conductive substrate 2 and a photosensitive layer 3. The single layer type photoreceptor as the photoreceptor 1 includes a single layer type photosensitive layer 3 c as the photosensitive layer 3. The single-layer type photosensitive layer 3 c is a single photosensitive layer 3.

  As shown in FIG. 4B, the single layer type photoreceptor as the photoreceptor 1 may include a conductive substrate 2, a single layer type photosensitive layer 3 c, and an intermediate layer (undercoat layer) 4. . The intermediate layer 4 is provided between the conductive substrate 2 and the single-layer type photosensitive layer 3c. Further, as shown in FIG. 4C, a protective layer 5 may be provided on the single-layer type photosensitive layer 3c.

  The thickness of the single-layer type photosensitive layer 3c is not particularly limited as long as the function as a single-layer type photosensitive layer can be sufficiently expressed. The thickness of the single-layer type photosensitive layer 3c is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less.

  The single-layer type photosensitive layer 3c as the photosensitive layer 3 contains a charge generating agent and a hole transporting agent in one layer. The single layer type photosensitive layer 3c may further contain one or more of an electron transport agent and a binder resin. The single-layer type photosensitive layer 3c may contain various additives as necessary. When the photoreceptor 1 is a single-layer photoreceptor, the charge generator, the hole transport agent, and the components added as necessary (for example, an electron transport agent, a binder resin, or an additive) It is contained in the photosensitive layer 3 (single-layer type photosensitive layer 3c). The structure of the photoreceptor 1 when the photoreceptor 1 is a single-layer photoreceptor has been described above with reference to FIG.

  Next, the elements of the multilayer photoreceptor and the single-layer photoreceptor that are photoreceptors will be described.

<3. Conductive substrate>
The conductive substrate is not particularly limited as long as it can be used as the conductive substrate of the photoreceptor. The conductive substrate may be formed of a material having at least a surface portion having conductivity. An example of the conductive substrate is a conductive substrate formed of a conductive material. Another example of the 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 materials having conductivity, aluminum or an aluminum alloy is preferable because charge transfer 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 or a drum shape. The thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.

<4. Hole transport agent>
The photosensitive layer contains the compound (1) according to the first embodiment as a hole transport agent. When the photoreceptor is a multilayer photoreceptor, the charge transport layer contains compound (1) as a hole transport agent. When the photoreceptor is a single layer type photoreceptor, the single layer type photosensitive layer contains the compound (1) as a hole transport agent. By containing the compound (1) in the photosensitive layer, as described in the first embodiment, the electrical characteristics of the photoreceptor can be improved.

  When the photoreceptor is a multilayer photoreceptor, the content of the compound (1) as the hole transport agent is 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the charge transport layer. It is preferable that it is 20 mass parts or more and 100 mass parts or less.

  When the photoreceptor is a single layer type photoreceptor, the content of the compound (1) as a hole transport agent is 10 parts by mass or more and 200 parts by mass with respect to 100 parts by mass of the binder resin contained in the single layer type photosensitive layer. The mass is preferably 10 parts by mass or more, more preferably 10 parts by mass or more and 100 parts by mass or less, and particularly preferably 10 parts by mass or more and 75 parts by mass or less.

  The charge transport layer may further contain another hole transport agent in addition to the compound (1). As another hole transport agent, for example, a nitrogen-containing cyclic compound or a condensed polycyclic compound other than the compound (1) can be used. Examples of the nitrogen-containing cyclic compound and the condensed polycyclic compound include diamine compounds (for example, N, N, N ′, N′-tetraphenylphenylenediamine derivatives, N, N, N ′, N′-tetraphenyl). Naphthylenediamine derivatives or N, N, N ′, N′-tetraphenylphenanthrylenediamine derivatives), oxadiazole compounds (for example, 2,5-di (4-methylaminophenyl) -1,3,4 -Oxadiazole), styryl compounds (for example, 9- (4-diethylaminostyryl) anthracene), carbazole compounds (for example, polyvinylcarbazole), organic polysilane compounds, pyrazoline compounds (for example, 1-phenyl-3- (p- Dimethylaminophenyl) pyrazolin), hydrazone compounds, indole compounds, oxazols System compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compound, or triazole-based compounds. The content of the compound (1) with respect to the total mass of the hole transport agent is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

<5. Charge generator>
When the photoreceptor is a multilayer photoreceptor, the charge generation layer contains a charge generation agent. When the photoreceptor is a single layer type photoreceptor, the single layer type photosensitive layer contains a charge generating agent.

  The charge generator is not particularly limited as long as it is a charge generator for a photoreceptor. Examples of the charge generator include phthalocyanine pigments, perylene pigments, bisazo pigments, trisazo pigments, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaraine pigments, indigo pigments, azurenium pigments, cyanine Pigments, inorganic photoconductive materials (for example, selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide or amorphous silicon), pyrylium pigments, ansanthrone pigments, triphenylmethane pigments, selenium pigments, toluidine pigments, Examples include pyrazoline pigments and quinacridone pigments. A charge generating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the phthalocyanine pigment include metal-free phthalocyanine or metal phthalocyanine represented by the chemical formula (C-1). Examples of the metal phthalocyanine include titanyl phthalocyanine, hydroxygallium phthalocyanine or chlorogallium phthalocyanine represented by the chemical formula (C-2). The phthalocyanine pigment may be crystalline or non-crystalline. The crystal shape of the phthalocyanine pigment (for example, α type, β type, Y type, V type or II type) is not particularly limited, and phthalocyanine pigments having various crystal shapes are used.

  Examples of the crystal of metal-free phthalocyanine include an X-type crystal of metal-free phthalocyanine (hereinafter sometimes referred to as X-type metal-free phthalocyanine). Examples of the crystal of titanyl phthalocyanine include α-type, β-type, and Y-type crystals of titanyl phthalocyanine (hereinafter sometimes referred to as α-type, β-type, or Y-type titanyl phthalocyanine). Examples of the crystal of hydroxygallium phthalocyanine include a V-type crystal of hydroxygallium phthalocyanine. Examples of chlorogallium phthalocyanine crystals include chlorogallium phthalocyanine type II crystals.

  For example, in a digital optical image forming apparatus (for example, a laser beam printer or a facsimile using a light source such as a semiconductor laser), it is preferable to use a photoreceptor having sensitivity in a wavelength region of 700 nm or more. Since it has a high quantum yield in a wavelength region of 700 nm or more, the charge generator is preferably a phthalocyanine pigment, more preferably a metal-free phthalocyanine or titanyl phthalocyanine, and even more preferably an X-type metal-free phthalocyanine or Y-type titanyl phthalocyanine. . In order to particularly improve the electrical characteristics when the photosensitive layer contains the compound (1) as a hole transport agent, Y-type titanyl phthalocyanine is more preferable as the charge generator.

  Y-type titanyl phthalocyanine has a main peak at 27.2 ° of the Bragg angle (2θ ± 0.2 °) in the CuKα characteristic X-ray diffraction spectrum, for example. The main peak in the CuKα characteristic X-ray diffraction spectrum is a peak having the first or second highest intensity in a range where the Bragg angle (2θ ± 0.2 °) is 3 ° or more and 40 ° or less.

  An example of a method for measuring the CuKα characteristic X-ray diffraction spectrum will be described. A sample (titanyl phthalocyanine) is filled in a sample holder of an X-ray diffractometer (for example, “RINT (registered trademark) 1100” manufactured by Rigaku Corporation), an X-ray tube Cu, a tube voltage 40 kV, a tube current 30 mA, and CuKα. An X-ray diffraction spectrum is measured under the condition of a characteristic X-ray wavelength of 1.542 mm. The measurement range (2θ) is, for example, 3 ° to 40 ° (start angle 3 °, stop angle 40 °), and the scanning speed is, for example, 10 ° / min.

  In a photoreceptor 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), an sanslon pigment is preferably used as a charge generating agent.

  When the photoreceptor is a multilayer photoreceptor, the content of the charge generating agent is preferably 5 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the base resin contained in the charge generation layer. More preferably, it is at least 500 parts by mass.

  When the photoreceptor is a single layer type photoreceptor, the content of the charge generating agent is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the single layer type photosensitive layer. It is preferably 0.5 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 4.5 parts by mass or less.

<6. Electron Transfer Agent and Electron Acceptor Compound>
When the photoreceptor is a multilayer photoreceptor, the charge transport layer may contain an electron acceptor compound as necessary. Thereby, there exists a tendency for the hole transport ability of a hole transport agent to improve. On the other hand, when the photosensitive member is a single layer type photosensitive member, the single layer type photosensitive layer may contain an electron transport agent, if necessary. Thereby, the single-layer type photosensitive layer can transport electrons, and it becomes easy to impart bipolar (bipolar) characteristics to the single-layer type photosensitive layer.

  Examples of electron transfer agents or 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, or dibromomaleic anhydride. Examples of quinone compounds include diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds, and dinitroanthraquinone compounds. An electron transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type. An electron acceptor compound may also be used individually by 1 type, and may be used in combination of 2 or more type.

  As an electron transfer agent or an electron acceptor, the compound represented by General formula (20) or (21) is mentioned, for example.

In general formulas (20) and (21), R _{20 to} R ₂₅ are each independently a hydrogen atom, a cyano group, an alkyl group that may have a substituent, or an alkenyl group that may have a substituent. Represents an alkoxy group that may have a substituent, an alkoxycarbonyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent.

The alkyl group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, a tert-butyl group, or a 1,1-dimethylpropyl group. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms which may further have a substituent, or a cyano group. The number of substituents is not particularly limited, but is preferably 3 or less. Examples of the substituent further included in the aryl group having 6 to 14 carbon atoms as the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, nitro group, cyano group, alkanoyl group having 2 to 7 carbon atoms (a group in which an alkyl group having 1 to 6 carbon atoms is bonded to a carbonyl group), benzoyl group, phenoxy group, 2 to 7 carbon atoms Examples include the following alkoxycarbonyl groups (groups in which an alkoxy group having 1 to 6 carbon atoms is bonded to a carbonyl group) or phenoxycarbonyl groups.

The alkenyl group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, a linear or branched, unsubstituted alkenyl group having 2 to 6 carbon atoms. . The alkenyl group having 2 to 6 carbon atoms has, for example, 1 to 3 double bonds. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a pentadienyl group, a hexenyl group, and a hexadienyl group. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a cyano group. The number of substituents is not particularly limited, but is preferably 3 or less.

The alkoxy group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, an alkoxy group having 1 to 6 carbon atoms. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group. The alkoxy group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a cyano group. As the substituent, a phenyl group is preferable. The number of substituents is not particularly limited, but is preferably 3 or less, more preferably 1.

The alkoxycarbonyl group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, an alkoxycarbonyl group having 2 to 7 carbon atoms. An alkoxycarbonyl group having 2 to 7 carbon atoms is a group in which a linear or branched, unsubstituted alkoxy group having 1 to 6 carbon atoms is bonded to a carbonyl group. The alkoxycarbonyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a cyano group. The number of substituents is not particularly limited, but is preferably 3 or less.

The aryl group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms is preferably a phenyl group. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkanoyl having 2 to 7 carbon atoms. A group (a group in which an alkyl group having 1 to 6 carbon atoms is bonded to a carbonyl group), a benzoyl group, a phenoxy group, an alkoxycarbonyl group having 2 to 7 carbon atoms (a carbonyl group having 1 to 6 carbon atoms) A group to which an alkoxy group is bonded), a phenoxycarbonyl group, an aryl group having 6 to 14 carbon atoms, or a biphenyl group. The number of substituents is not particularly limited, but is preferably 3 or less.

The heterocyclic group represented by R _{20 to} R ₂₅ in the general formulas (20) and (21) is, for example, 5-membered or 6 containing one or more heteroatoms selected from the group consisting of N, S and O A monocyclic heterocyclic group having a member; a heterocyclic group in which such single rings are condensed; or a heterocyclic group in which such a single ring is condensed with a 5-membered or 6-membered hydrocarbon ring. When the heterocyclic group is a condensed ring, the number of rings contained in the condensed ring is preferably 2 or 3. Examples of the substituent that the heterocyclic group may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, Alkanoyl group having 2 to 7 carbon atoms (a group in which an alkyl group having 1 to 6 carbon atoms is bonded to a carbonyl group), benzoyl group, phenoxy group, alkoxycarbonyl group having 2 to 7 carbon atoms (carbonyl group) Group having an alkoxy group having 1 to 6 carbon atoms bonded thereto, or a phenoxycarbonyl group. The number of substituents is not particularly limited, but is preferably 3 or less.

  Specific examples of the compound represented by the general formula (20) include a compound represented by the chemical formula (E-1). Specific examples of the compound represented by the general formula (21) include a compound represented by the chemical formula (E-2). Hereinafter, the compounds represented by the chemical formulas (E-1) and (E-2) may be referred to as compounds (E-1) and (E-2), respectively.

  When the photoreceptor is a multilayer photoreceptor, the content of the electron acceptor compound is preferably 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the charge transport layer. More preferably, it is 0.5 parts by mass or more and 10 parts by mass or less.

  When the photoreceptor is a single layer type photoreceptor, the content of the electron transport agent is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the single layer type photosensitive layer. Preferably, it is 10 to 80 parts by mass, more preferably 30 to 50 parts by mass.

<7. Binder resin>
When the photoreceptor is a multilayer photoreceptor, the charge transport layer contains a binder resin. When the photoreceptor is a single layer type photoreceptor, the single layer type photosensitive layer contains a binder resin.

  Examples of the binder resin include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Examples of the thermoplastic resin include polycarbonate resin, polyarylate resin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic acid polymer, styrene-acrylic acid copolymer, 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. As a thermosetting resin, a silicone resin, an epoxy resin, a phenol resin, a urea resin, or a melamine resin is mentioned, for example. Examples of the photocurable resin include epoxy acrylate (epoxy compound acrylic acid adduct) or urethane-acrylate (urethane compound acrylic acid adduct). These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these resins, a polycarbonate resin is preferable because a single-layer type photosensitive layer and a charge transport layer excellent in balance of workability, mechanical properties, optical properties, and abrasion resistance can be obtained. Examples of the polycarbonate resin include bisphenol Z type polycarbonate resin, bisphenol ZC type polycarbonate resin, bisphenol C type polycarbonate resin and bisphenol A type polycarbonate resin represented by the following chemical formula.

  The viscosity average molecular weight of the binder resin is preferably 40,000 or more, and more preferably 40,000 or more and 52,500 or less. When the viscosity average molecular weight of the binder resin is 40,000 or more, it is easy to improve the wear resistance of the photoreceptor. When the viscosity average molecular weight of the binder resin is 52,500 or less, the binder resin is easily dissolved in a solvent during formation of the photosensitive layer, and the viscosity of the charge transport layer coating solution or single layer type photosensitive layer coating solution is increased. Not too much. As a result, it becomes easy to form a charge transport layer or a single-layer type photosensitive layer.

<8. Base resin>
When the photoreceptor is a multilayer photoreceptor, the charge generation layer contains a base resin. The base resin is not particularly limited as long as it is a base resin applicable to the photoreceptor. Examples of the base resin include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Examples of the thermoplastic resin include styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-acrylic acid copolymer, acrylic acid polymer, polyethylene resin, ethylene-vinyl acetate. Copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide resin, urethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin , Ketone resin, polyvinyl butyral resin, polyether resin or polyester resin. Examples of the thermosetting resin include silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, and other crosslinkable thermosetting resins. Examples of the photocurable resin include epoxy acrylate (epoxy compound acrylic acid adduct) or urethane-acrylate (urethane compound acrylic acid adduct). A base resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The base resin contained in the charge generation layer is preferably different from the binder resin contained in the charge transport layer. In the production of a multilayer photoreceptor, for example, a charge generation layer is formed on a conductive substrate, and a charge transport layer is formed on the charge generation layer. At that time, a charge transport layer coating solution is applied onto the charge generation layer. Therefore, the charge generation layer is preferably not dissolved in the solvent of the charge transport layer coating solution.

<9. Additives>
The photosensitive layer (charge generation layer, charge transport layer or single layer type photosensitive layer) of the photoreceptor may contain various additives as required. Examples of additives include deterioration inhibitors (for example, antioxidants, radical scavengers, singlet quenchers or ultraviolet absorbers), softeners, surface modifiers, extenders, thickeners, dispersion stabilizers. , Waxes, acceptors, donors, surfactants, plasticizers, sensitizers or leveling agents. Antioxidants include, for example, hindered phenols (eg, di (tert-butyl) p-cresol), hindered amines, paraphenylenediamine, arylalkanes, hydroquinones, spirochromans, spirodanone or derivatives thereof, organic sulfur compounds or An organic phosphorus compound is mentioned.

<10. Intermediate layer>
The intermediate layer (undercoat layer) contains, for example, inorganic particles and a resin (intermediate layer resin) used for the intermediate layer. The presence of the intermediate layer is considered to suppress the increase in resistance by smoothing the flow of current generated when the photosensitive member is exposed while maintaining an insulating state capable of suppressing the occurrence of leakage.

  Examples of the inorganic particles include metal (for example, aluminum, iron or copper), metal oxide (for example, titanium oxide, alumina, zirconium oxide, tin oxide or zinc oxide) particles or non-metal oxide (for example, silica). Particles. These inorganic particles may be used individually by 1 type, and may use 2 or more types together.

  The resin for the intermediate layer is not particularly limited as long as it can be used as a resin for forming the intermediate layer. The intermediate layer may contain various additives. The additive is the same as the additive for the photosensitive layer.

<11. Photoconductor manufacturing method>
When the photoreceptor is a multilayer photoreceptor, the multilayer photoreceptor is manufactured, for example, as follows. First, a charge generation layer coating solution and a charge transport layer coating solution are prepared. A charge generation layer is formed by applying a coating solution for charge generation layer onto a conductive substrate and drying. Subsequently, the charge transport layer coating liquid is applied on the charge generation layer and dried to form the charge transport layer. Thereby, a laminated photoreceptor is manufactured.

  The coating solution for the charge generation layer is prepared by dissolving or dispersing the charge generation agent and components added as necessary (for example, base resin and various additives) in a solvent. The coating solution for the charge transport layer is prepared by dissolving or dispersing a hole transport agent and components added as necessary (for example, a binder resin, an electron acceptor compound, and various additives) in a solvent.

  Next, when the photoconductor is a single layer type photoconductor, the single layer type photoconductor is manufactured, for example, as follows. The single-layer type photoreceptor is manufactured by applying a coating solution for a single-layer type photosensitive layer onto a conductive substrate and drying it. The coating solution for a single-layer type photosensitive layer is obtained by dissolving or dispersing a charge generating agent, a hole transporting agent and components added as necessary (for example, an electron transporting agent, a binder resin and various additives) in a solvent. Manufactured by.

  The solvent contained in the coating solution (charge generating layer coating solution, charge transport layer coating solution or single layer type photosensitive layer coating solution) is not particularly limited as long as each component contained in the coating solution can be dissolved or dispersed. . Examples of solvents include alcohols (eg, methanol, ethanol, isopropanol or butanol), aliphatic hydrocarbons (eg, n-hexane, octane or cyclohexane), aromatic hydrocarbons (eg, benzene, toluene or xylene), Halogenated hydrocarbons (eg dichloromethane, dichloroethane, carbon tetrachloride or chlorobenzene), ethers (eg dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or propylene glycol monomethyl ether), ketones (eg acetone, Methyl ethyl ketone or cyclohexanone), esters (eg ethyl acetate or methyl acetate), dimethylformaldehyde, dimethylform Amide or dimethyl sulfoxide. These solvents are used alone or in combination of two or more. In order to improve the workability during the production of the photoreceptor, it is preferable to use a non-halogen solvent (a solvent other than the halogenated hydrocarbon) as the solvent.

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

  The coating solution (charge generating layer coating solution, charge transport layer coating solution or single layer photosensitive layer coating solution) may contain, for example, a surfactant in order to improve the dispersibility of each component. .

  As a method of applying a coating solution (a coating solution for a charge generation layer, a coating solution for a charge transport layer or a coating solution for a single-layer type photosensitive layer), as long as the coating solution can be uniformly applied on a conductive substrate, There is no particular limitation. 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 drying the coating solution (charge generating layer coating solution, charge transport layer coating solution or single layer type photosensitive layer coating solution) is not particularly limited as long as the solvent in the coating solution can be evaporated. For example, the method of heat-processing (hot-air drying) is mentioned using a high-temperature dryer or a vacuum dryer. The heat treatment conditions are, for example, a temperature of 40 ° C. or higher and 150 ° C. or lower and a time of 3 minutes or longer and 120 minutes or shorter.

  In addition, the manufacturing method of a photoreceptor may further include one or both of a step of forming an intermediate layer and a step of forming a protective layer as necessary. A known method is appropriately selected in the step of forming the intermediate layer and the step of forming the protective layer.

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

<1. Photosensitive Material>
The following hole transporting agent and charge generating agent were prepared as materials for forming the charge generating layer and charge transporting layer of the multilayer photoreceptor. The following hole transporting agent, charge generating agent and electron transporting agent were prepared as materials for forming the single layer type photosensitive layer of the single layer type photoreceptor.

<1-1. Hole transport agent>
As hole transporting agents, the compounds (H-1) to (H-5) described in the first embodiment were prepared. Compounds (H-1) to (H-5) were each produced by the following method.

<1-1-1. Production of Compounds (6a) to (6c)>
First, compounds (6a) to (6c) were produced as raw materials for producing compounds (H-1) to (H-5). Compound (6c) was produced according to the following reactions (R-11) and (R-12). Compound (6a) was produced according to the following reactions (R-11) and (R-13). Compound (6b) was produced according to the following reactions (R-14) and (R-15).

  In reaction (R-11), compound (3a) was obtained by reacting compound (2a) with triethyl phosphite. Specifically, 16.1 g (0.10 mol) of the compound (2a) and 25.0 g (0.15 mol) of triethyl phosphite were charged into a 200-mL flask. The flask contents were stirred at 180 ° C. for 8 hours and then cooled to room temperature. Subsequently, unreacted triethyl phosphite contained in the flask contents was distilled off under reduced pressure. This obtained the compound (3a) which is a white liquid. The yield of compound (3a) was 24.1 g, and the yield of compound (3a) from compound (2a) was 92 mol%.

  In reaction (R-12), compound (3a) was reacted with compound (4a) to give compound (6c). Reaction (R-12) is a Wittig reaction. Specifically, 13.1 g (0.05 mol) of the compound (3a) obtained in the reaction (R-11) was added to a two-necked flask having a volume of 500 mL at 0 ° C. The air in the flask was replaced with argon gas. Subsequently, dry tetrahydrofuran (100 mL) and 9.3 g (0.05 mol) of 28% sodium methoxide were added to the flask. The flask contents were stirred for 30 minutes. Subsequently, a solution of 7.0 g (0.05 mol) of compound (4a) in dry tetrahydrofuran (300 mL) was added to the flask. The flask contents were stirred at room temperature for 12 hours. The contents of the flask were poured into ion exchange water and extracted with toluene. The obtained organic layer was washed 5 times with ion-exchanged water and dried using anhydrous sodium sulfate. Subsequently, the solvent contained in the organic layer was distilled off to obtain a residue. The obtained residue was crystallized using toluene / methanol (20 mL / 100 mL). This obtained the compound (6c). The yield of compound (6c) was 9.4 g, and the yield of compound (6c) from compound (3a) was 75 mol%.

  In the reaction (R-13), the compound (3a) and the compound (5a) were reacted to obtain the compound (6a). Reaction (R-13) is a Wittig reaction. Specifically, 13.1 g (0.05 mol) of the compound (3a) obtained in the reaction (R-11) was added to a two-necked flask having a volume of 500 mL at 0 ° C. The air in the flask was replaced with argon gas. Subsequently, dry tetrahydrofuran (100 mL) and 9.3 g (0.05 mol) of 28% sodium methoxide were added to the flask. The flask contents were stirred for 30 minutes. Subsequently, a solution of 8.4 g (0.05 mol) of compound (5a) in dry tetrahydrofuran (300 mL) was added to the flask. The flask contents were stirred at room temperature for 12 hours. The contents of the flask were poured into ion exchange water and extracted with toluene. The obtained organic layer was washed 5 times with ion-exchanged water and dried using anhydrous sodium sulfate. Subsequently, the solvent contained in the organic layer was distilled off to obtain a residue. The obtained residue was crystallized using toluene / methanol (20 mL / 100 mL). This obtained the compound (6a) which is a white crystal. The yield of compound (6a) was 9.6 g, and the yield of compound (6a) from compound (3a) was 69 mol%.

  In reaction (R-14), compound (7a) was reacted with triethyl phosphite to obtain compound (8). Specifically, 15.2 g (0.05 mol) of the compound (7a) and 25.0 g (0.15 mol) of triethyl phosphite were charged into a 200-mL flask. The flask contents were stirred at 180 ° C. for 8 hours and then cooled to room temperature. Subsequently, unreacted triethyl phosphite contained in the flask contents was distilled off under reduced pressure. This obtained compound (8). The yield of compound (8) was 14.5 g, and the yield of compound (8) from compound (7a) was 88 mol%.

  In the reaction (R-15), the compound (8) and the compound (4a) were reacted to obtain the compound (6b). Reaction (R-15) is a Wittig reaction. Specifically, 16.4 g (0.05 mol) of the compound (8) obtained in the reaction (R-14) was added to a 500 mL two-necked flask at 0 ° C. The air in the flask was replaced with argon gas. Subsequently, dry tetrahydrofuran (100 mL) and 9.3 g (0.05 mol) of 28% sodium methoxide were added to the flask. The flask contents were stirred for 30 minutes. Subsequently, a dry tetrahydrofuran (300 mL) solution of 14.1 g (0.10 mol) of the compound (4a) was added to the flask. The flask contents were stirred at room temperature for 12 hours. The contents of the flask were poured into ion exchange water and extracted with toluene. The obtained organic layer was washed 5 times with ion-exchanged water and dried using anhydrous sodium sulfate. Subsequently, the solvent contained in the organic layer was distilled off to obtain a residue. The obtained residue was crystallized using toluene / methanol (20 mL / 100 mL). This obtained the compound (6b). The yield of compound (6b) was 3.8 g, and the yield of compound (6b) from compound (8) was 25 mol%.

<1-1-2. Production of Compounds (12a) and (12b)>
Next, compounds (12a) and (12b) were produced as raw materials for producing the compounds (14a) to (14e). Compound (12a) was produced according to the following reaction (R-16). Compound (12b) was produced according to the following reaction (R-17).

  In the reaction (R-16), the compound (12a) was obtained by reacting the compound (10a) with the compound (11a). Specifically, 6.3 g (0.0450 mol) of the compound (10a), 10.0 g (0.0450 mol) of the compound (11a, diphenylhydrazine hydrochloride), toluene (100 mL) and p-toluene were added to the Dean-Stark tube. Sulfonic acid (0.0045 mol) was added. The mixture was stirred at reflux at 100 ° C. for 4 hours. The resulting mixture was poured into ion exchange water and extracted with toluene. The obtained organic layer was washed 5 times with ion exchange water and dried over anhydrous sodium sulfate, and then the solvent was distilled off. The obtained residue was crystallized from toluene / methanol (volume ratio 1: 1) to obtain a compound (12a) as white crystals. The yield of the compound (12a) was 12.1 g, and the yield of the compound (12a) from the compound (10a) was 88 mol%.

  In the reaction (R-17), the compound (10b) and the compound (11a) were reacted to obtain the compound (12b). Reaction (R-17) was carried out in the same manner as reaction (R-16) except that 7.5 g (0.0450 mol) of compound (10b) was used instead of 6.3 g (0.0450 mol) of compound (10a). The same method was used. As a result, compound (12b) was obtained. The yield of compound (12b) was 11.8 g, and the yield of compound (12b) from compound (10b) was 79 mol%.

<1-1-3. Production of Compounds (14a) to (14e)>
Next, compound (14a) was produced according to the following reaction (R-18).

In the reaction (R-18), the compound (12a) and the compound (13a) were reacted to obtain the compound (14a). Hereinafter, the compound (12a) may be described as a first raw material for the reaction (R-18), and the compound (13a) may be described as a second raw material for the reaction (R-18). Reaction (R-18) is a coupling reaction. Specifically, in a three-necked flask, 6.1 g (0.020 mol) of the compound (12a), 0.0662 g (1.89 × 10 ⁻⁴ mol) of tricyclohexylphosphine, tris (dibenzylideneacetone) dipalladium (0) 0 0.0864 g (9.44 × 10 ⁻⁵ mol), sodium tert-butoxide 4.0 g (0.042 mol), compound (13a) 2.1 g (0.020 mol) and distilled о-xylene (500 mL). I put it in. The air in the flask was replaced with argon gas. Subsequently, the flask contents were stirred at 120 ° C. for 5 hours and then cooled to room temperature. The contents of the flask were washed with ion exchange water three times to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, followed by drying treatment and adsorption treatment. The organic layer after drying treatment and adsorption treatment was distilled off under reduced pressure to remove о-xylene. This gave a residue. The obtained residue was crystallized using chloroform / hexane (volume ratio 1: 1). Thereby, a compound (14a) was obtained as a reaction product of the reaction (R-18). The yield of compound (14a) was 5.1 g, and the yield of compound (14a) from compound (12a) was 69 mol%.

  Compounds (14b) to (14e) were produced in the same manner as in the production of compound (14a) except that the following points were changed. In addition, each raw material used in manufacture of compound (14b)-(14e) was added by the same mole number as the mole number of the corresponding raw material used in manufacture of compound (14a).

  The first raw material for the reaction (R-18) was changed from the compound (12a) in the production of the compound (H-1) to the first raw material (compound (12a) or (12b)) shown in Table 1. The second raw material for the reaction (R-18) is converted from the compound (13a) in the production of the compound (H-1) to the second raw material (compound (13b), (13c), (13d) or (13e) shown in Table 1. )). As a result, any one of the compounds (14b), (14c), (14d) and (14e) was obtained as a reaction product of the reaction (R-18) instead of the compound (14a). Table 1 shows the yields of the compounds (14b), (14c), (14d) and (14e) obtained in the reaction (R-18). Table 1 shows the yields of the compounds (14b), (14c), (14d) and (14e) from the first raw material (compound (12a) or (12b)).

  In Table 1, compounds (12a) and (12b), (13a) to (13e), and (14a) to (14e) are represented by the following chemical formulas (12a) and (12b), (13a) to (13e), respectively. And (14a) to (14e).

<1-1-4. Production of Compounds (H-1) to (H-5)>
Next, compound (H-1) was produced according to the following reaction (R-19).

In reaction (R-19), compound (6a) was reacted with compound (14a) to give compound (H-1). Hereinafter, the compound (6a) may be described as a first raw material for the reaction (R-19), and the compound (14a) may be described as a second raw material for the reaction (R-19). Reaction (R-19) is a coupling reaction. Specifically, in a three-necked flask, 1.40 g (0.005 mol) of the compound (6a) obtained in the reaction (R-13), 0.0356 g (1.02 × 10 ⁻⁴ mol) of tricyclohexylphosphine, tris ( Dibenzylideneacetone) dipalladium (0) 0.0465 g (5.09 × 10 ⁻⁵ mol), sodium tert-butoxide 1.00 g (0.010 mol), compound (14a) obtained by reaction (R-18) 3.60 g (0.010 mol) and distilled о-xylene (200 mL) were charged. The air in the flask was replaced with argon gas. Subsequently, the flask contents were stirred at 120 ° C. for 5 hours and then cooled to room temperature. The contents of the flask were washed with ion exchange water three times to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, followed by drying treatment and adsorption treatment. The organic layer after drying treatment and adsorption treatment was distilled off under reduced pressure to remove о-xylene. This gave a residue. The obtained residue was crystallized using chloroform / hexane (volume ratio 1: 1). As a result, compound (H-1) was obtained. The yield of compound (H-1) was 3.2 g, and the yield of compound (H-1) from compound (6a) was 66 mol%.

  Compounds (H-2) to (H-5) were produced in the same manner as in the production of compound (H-1) except that the following points were changed. In addition, each raw material used in manufacture of compound (H-2)-(H-5) was added by the same mole number as the mole number of the corresponding raw material used in manufacture of compound (H-1).

  The first raw material for the reaction (R-19) was changed from the compound (6a) in the production of the compound (H-1) to the first raw material (compound (6a), (6b) or (6c)) shown in Table 2. did. The second raw material for the reaction (R-19) is converted from the compound (14a) in the production of the compound (H-1) to the second raw material (compound (14b), (14c), (14d) or (14e) shown in Table 1. )). As a result, as a reaction product of reaction (R-19), instead of compound (H-1), compounds (H-2), (H-3), (H-4) and (H-5) Either was obtained. Table 2 shows the yields of the compounds (H-2), (H-3), (H-4) and (H-5) obtained in the reaction (R-19). Moreover, the yield of the compound (H-2), (H-3), (H-4) and (H-5) from the first raw material (compound (6a), (6b) or (6c)) is shown. It is shown in 2.

Next, with reference to ¹ H-NMR (proton nuclear magnetic resonance spectroscopy), it was analyzed by ¹ H-NMR spectrum of the compound prepared (H-1) ~ (H -5). The magnetic field strength was set to 300 MHz. Deuterated chloroform (CDCl ₃ ) was used as the solvent. Tetramethylsilane (TMS) was used as an internal standard substance.

As representative examples of the compounds (H-1) to (H-5), ¹ H-NMR spectra of the compounds (H-2) and (H-4) are shown in FIGS. The chemical shift values of ¹ H-NMR spectra of compounds (H-2) and (H-4) are shown below. In addition, the peak around 1.50 ppm in FIGS. 1 and 2 is a peak derived from water remaining in the compounds (H-2) and (H-4).
Compound (H-2): ¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.35-7.42 (m, 8H), 7.11-7.25 (m, 22H), 6.83-7 .06 (m, 16H), 6.72-6.80 (m, 4H), 6.41 (d, 2H), 3.80 (s, 6H), 2.01 (s, 6H).
Compound (H-4): ¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.35-7.42 (m, 8H), 7.11-7.24 (m, 20H), 6.82-7 .06 (m, 20H), 6.41 (d, 2H), 2.33 (s, 6H), 1.99 (s, 6H).

^{From the 1} H-NMR spectrum and the chemical shift value, it was confirmed that the compounds (H-2) and (H-4) were obtained. The other compounds (H-1), (H-3) and (H-5) were similarly analyzed by the ¹ H-NMR spectrum and the chemical shift value, respectively, for the compounds (H-1), (H-3) and It was confirmed that (H-5) was obtained.

<1-1-5. Preparation of compounds (HA) and (H-B)>
As hole transporting agents, compounds represented by the following chemical formulas (HA) and (H-B) were also prepared. Hereinafter, the compounds represented by the chemical formulas (HA) and (H-B) may be referred to as compounds (HA) and (H-B), respectively.

<1-2. Charge generator>
Compounds (C-1X) and (C-2Y) were prepared as charge generators. The compound (C-1X) was a metal-free phthalocyanine represented by the chemical formula (C-1) described in the second embodiment. In addition, the crystal structure of the compound (C-1X) was X type.

  The compound (C-2Y) was titanyl phthalocyanine represented by the chemical formula (C-2) described in the second embodiment. The crystal structure of the compound (C-2Y) was Y type.

<1-3. Electron transport agent>
The compounds (E-1) and (E-2) described in the second embodiment were prepared as electron transport agents to be contained in the single layer type photosensitive layer of the single layer type photoreceptor.

<2. Manufacture of multilayer photoconductor>
Using the material for forming the photosensitive layer described above, multilayer photoreceptors (P-1) to (P-7) were produced.

<2-1. Manufacture of multilayer photoconductor (P-1)>
Surface-treated titanium oxide (“Prototype SMT-02” manufactured by Teika Co., Ltd., number average primary particle size 10 nm) was prepared. Specifically, titanium oxide was surface-treated with alumina and silica, and the surface-treated titanium oxide was further surface-treated with methylhydrogenpolysiloxane while being wet-dispersed.

  Next, an undercoat layer coating solution was prepared. Specifically, 2.8 parts by mass of surface-treated titanium oxide, 1 part by mass of a copolymerized polyamide resin (“Daiamide X4585” manufactured by Daicel-Evonik Co., Ltd.), 10 parts by mass of ethanol and a solvent as a solvent 2 parts by weight of butanol was added. The contents of the container were mixed for 5 hours using a bead mill to disperse the material in the solvent. This obtained the coating liquid for undercoat layers.

  Next, an undercoat layer was formed. Specifically, the obtained undercoat layer coating solution was filtered using a 5 μm filter. Thereafter, the coating solution for the undercoat layer was applied to the surface of an aluminum drum-shaped support (diameter 30 mm, total length 238.5 mm) as a conductive substrate by using a dip coating method. Subsequently, the applied coating solution for undercoat layer was heated at 130 ° C. for 30 minutes. Thereby, an undercoat layer (film thickness: 1.5 μm) was formed on the conductive substrate.

  Next, a coating solution for charge generation layer was prepared. Specifically, in a container, 1 part by mass of a compound (C-2Y) as a charge generating agent, 1 part by mass of a polyvinyl butyral resin (“Denka Butyral # 6000EP” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a base resin, dispersed 40 parts by mass of propylene glycol monomethyl ether as a medium and 40 parts by mass of tetrahydrofuran as a dispersion medium were added. The contents of the container were mixed for 2 hours using a bead mill to disperse the material in the dispersion medium. This obtained the coating liquid for charge generation layers. Next, the obtained coating solution for charge generation layer was filtered using a 3 μm filter. Thereafter, a coating solution for charge generation layer was applied onto the formed undercoat layer using a dip coating method. Subsequently, the applied charge generation layer coating solution was dried at 50 ° C. for 5 minutes. As a result, a charge generation layer (film thickness: 0.3 μm) was formed on the undercoat layer.

  Next, a charge transport layer coating solution was prepared. Specifically, 70 parts by mass of the compound (H-1) as a hole transport agent, bisphenol Z type polycarbonate resin as a binder resin (“Panlite (registered trademark) TS-2050” manufactured by Teijin Ltd., viscosity average molecular weight) 50,000) 100 parts by mass, di (tert-butyl) p-cresol (BHT) 5 parts by mass, tetrahydrofuran 430 parts by mass as a solvent and toluene 430 parts by mass as a solvent were put into a container. . The contents of the container were mixed and the material was dissolved in the solvent. This obtained the coating liquid for charge transport layers. Next, the obtained charge transport layer coating solution was applied onto the formed charge generation layer in the same manner as the charge generation layer coating solution. Subsequently, the applied charge transport layer coating solution was dried at 130 ° C. for 30 minutes. As a result, a charge transport layer (film thickness 20 μm) was formed on the charge generation layer. As a result, a multilayer photoreceptor (P-1) was obtained.

<2-2. Production of Laminated Photoconductors (P-2) to (P-7)>
The laminated photoreceptors (P-2) to (P-7) were produced in the same manner as in the production of the laminated photoreceptor (P-1) except that the following points were changed. The compound (H-1) as the hole transporting agent used in the production of the multilayer photoreceptor (P-1) was changed to the type of hole transporting agent shown in Table 3.

<3. Manufacture of single layer type photoreceptor>
Single layer type photoreceptors (P-8) to (P-28) were produced using materials for forming the photosensitive layer.

<3-1. Manufacture of single layer type photoreceptor (P-8)>
In the container, 5 parts by mass of the compound (C-1X) as a charge generating agent, 80 parts by mass of the compound (H-1) as a hole transporting agent, 50 parts by mass of the compound (E-1) as an electron transporting agent, 100 parts by mass of bisphenol Z-type polycarbonate resin (“Panlite (registered trademark) TS-2050” manufactured by Teijin Ltd., viscosity average molecular weight 50,000) as a binder resin and 800 parts by mass of tetrahydrofuran as a solvent were added. The contents of the container were mixed for 50 hours using a ball mill to disperse the material in the solvent. This obtained the coating liquid for single layer type photosensitive layers. The single layer type photosensitive layer coating solution was coated on an aluminum drum-shaped support (diameter: 30 mm, total length: 238.5 mm) as a conductive substrate using a dip coating method. The applied coating liquid for single layer type photosensitive layer was dried with hot air at 100 ° C. for 30 minutes. Thereby, a single-layer type photosensitive layer (film thickness: 25 μm) was formed on the conductive substrate. As a result, a single layer type photoreceptor (P-8) was obtained.

<3-2. Production of Single Layer Type Photoreceptors (P-9) to (P-28)>
Single-layer photoconductors (P-9) to (P-28) were produced in the same manner as in the production of the single-layer photoconductor (P-8) except that the following points were changed. The compound (C-1X) as the charge generating agent used in the production of the single layer type photoreceptor (P-8) was changed to the type of charge generating agent shown in Table 4. The compound (H-1) as the hole transporting agent used in the production of the single layer type photoreceptor (P-8) was changed to the kind of hole transporting agent shown in Table 4. The compound (E-1) as the electron transport agent used for the production of the single-layer type photoreceptor (P-8) was changed to the type of electron transport agent shown in Table 4.

<4. Evaluation of electrical characteristics of multilayer photoconductor>
The electrical characteristics were evaluated for each of the produced laminated photoreceptors (P-1) to (P-7). The electrical characteristics were evaluated in an environment at a temperature of 23 ° C. and a relative humidity of 60% RH. First, the surface of the multilayer photoreceptor was charged to −700 V using a drum sensitivity tester (manufactured by Gentec Corporation). Next, monochromatic light (wavelength 780 nm, half-value width 20 nm, light energy 0.4 μJ / cm ² ) was extracted from the white light of the halogen lamp using a bandpass filter. The extracted monochromatic light was irradiated on the surface of the multilayer photoreceptor. The surface potential of the laminated photoreceptor was measured after 0.5 seconds had elapsed from the end of irradiation. The measured surface potential was defined as a sensitivity potential (V _L , unit V). Table 3 shows the measured sensitivity potential (V _L ) of the laminated photoreceptor. Note that the smaller the absolute value of the sensitivity potential (V _L ), the more excellent the electrical characteristics of the laminated photoreceptor.

<5. Evaluation of electrical characteristics of single-layer type photoreceptor>
The electrical characteristics of each of the produced single layer type photoreceptors (P-8) to (P-28) were evaluated. The electrical characteristics were evaluated in an environment with a temperature of 23 ° C. and a humidity of 60% RH. First, the surface of the single layer type photoreceptor was charged to +700 V using a drum sensitivity tester (manufactured by Gentec Corporation). Next, monochromatic light (wavelength 780 nm, half-value width 20 nm, light energy 1.5 μJ / cm ² ) was extracted from the white light of the halogen lamp using a bandpass filter. The surface of the monolayer type photoreceptor was irradiated with the extracted monochromatic light. The surface potential of the single-layer photoreceptor was measured after 0.5 seconds had elapsed from the end of irradiation. The measured surface potential was defined as a sensitivity potential (V _L , unit V). Table 4 shows the measured sensitivity potential (V _L ) of the single-layer type photoreceptor. Note that the smaller the absolute value of the sensitivity potential (V _L ), the better the electrical characteristics of the single layer type photoreceptor.

<6. Evaluation of crystallization of photoconductor>
For each of the multilayer photoconductors (P-1) to (P-5), the surface of the multilayer photoconductor was visually observed to evaluate the presence or absence of crystallization. For each of the single-layer photoreceptors (P-8) to (P-22), the surface of the single-layer photoreceptor was visually observed to evaluate the presence or absence of crystallization. As a result, no crystallization was confirmed in any of the multilayer photoreceptors (P-1) to (P-5) and the single-layer photoreceptors (P-8) to (P-22).

In Tables 3 and 4, CGM, HTM, ETM, and _VL represent a charge generator, a hole transport agent, an electron transport agent, and a sensitivity potential, respectively.

The photosensitive layers of the multilayer photoreceptors (P-1) to (P-5) and the single-layer photoreceptors (P-8) to (P-22) are specifically composed of the compound (1) as a hole transport agent. Contained any of compounds (H-1) to (H-5). Therefore, as is apparent from Tables 3 and 4, these photoreceptors have a small absolute value of the sensitivity potential (V _L ) and excellent electrical characteristics.

On the other hand, the photosensitive layers of the multilayer photoreceptors (P-6) to (P-7) and the single-layer photoreceptors (P-23) to (P-28) have the compound (1) as a hole transport agent. It did not contain. Therefore, as apparent from Tables 3 and 4, in these photoreceptors, the absolute value of the sensitivity potential (V _L ) was large and the electrical characteristics were inferior.

  From the above, it was shown that the compound (1) improves the electrical characteristics of the photoreceptor when contained in the photosensitive layer. Moreover, it was shown that a photoreceptor provided with a photosensitive layer containing the compound (1) is excellent in electrical characteristics.

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

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Conductive base | substrate 3 Photosensitive layer 3a Charge generation layer 3b Charge transport layer 3c Single layer type photosensitive layer

Claims (7)

A compound represented by the following general formula (1).

In the general formula (1),
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently have a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent. An alkoxy group having 1 to 6 carbon atoms which may be substituted or an aryl group having 6 to 14 carbon atoms which may have a substituent;
a represents an integer of 1 to 3, b and c each independently represent 0 or 1,
d, e, f, g, h and i each independently represent an integer of 0 to 5, and when d represents an integer of 2 to 5, a plurality of R ₁ may be the same or different. A plurality of R _{2 s} may be the same or different when e represents an integer of 2 to 5, and a plurality of R _{3 s} may be the same or different when f represents an integer of 2 to 5. When R represents an integer of 2 or more and 5 or less, the plurality of R ₄ may be the same or different, and when h represents an integer of 2 or more and 5 or less, the plurality of R ₅ may be the same or different, and i is 2 When an integer of 5 or less is represented, a plurality of R ₆ may be the same or different. In the general formula (1), the group represented by the following general formula (1-1) is the same as the group represented by the following general formula (1-2).

In the general formula (1-1),
R ₁ , R ₂ and R ₃ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Represents an aryl group having 6 to 14 carbon atoms, which may have 6 or less alkoxy groups or substituents,
b represents 0 or 1,
d, e and f each independently represent an integer of 0 to 5, and when d represents an integer of 2 to 5, a plurality of R _{1 s} may be the same or different, and e is 2 to 5 A plurality of R ₂ may be the same or different when the following integers are represented, and a plurality of R ₃ may be the same or different when f represents an integer of 2 to 5.
Y ₁ represents a binding site;
In the general formula (1-2),
R ₄ , R ₅ and R ₆ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or 1 or more carbon atoms which may have a substituent. Represents an aryl group having 6 to 14 carbon atoms, which may have 6 or less alkoxy groups or substituents,
c represents 0 or 1,
g, h, and i each independently represent an integer of 0 to 5, and when g represents an integer of 2 to 5, a plurality of R ₄ may be the same or different, and h is 2 to 5. A plurality of R ₅ may be the same or different when the following integers are represented, and a plurality of R ₆ may be the same or different when i represents an integer of 2 to 5.
Y ₂ represents a binding site. In the general formula (1),
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 carbon atoms. Represents an aryl group of 14 or less,
The compound according to claim 1 or 2, wherein d, e, f, g, h and i each independently represents an integer of 0 or more and 2 or less.   The compound as described in any one of Claims 1-3 in which a represents 2 or 3 in the said General formula (1). The compound represented by the general formula (1) is a compound represented by the following chemical formula (H-1), (H-2), (H-3), (H-4) or (H-5). The compound according to any one of claims 1 to 3.

An electrophotographic photoreceptor having a photosensitive layer,
The said photosensitive layer is an electrophotographic photoreceptor containing the compound as described in any one of Claims 1-5. A conductive substrate;
The photosensitive layer contains at least a charge generator and a hole transport agent,
The photosensitive layer includes a charge generation layer containing the charge generation agent and a charge transport layer containing the hole transport agent, or
The photosensitive layer is a single-layer type photosensitive layer containing the charge generating agent and the hole transport agent in one layer,
The electrophotographic photoreceptor according to claim 6, wherein the compound is contained as the hole transport agent.

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