JP6059693B2 - Electrophotographic photoreceptor - Google Patents

Description

  The present invention relates to a triarylamine derivative and an electrophotographic photoreceptor.

  An electrophotographic photosensitive member is used as an image carrier in an electrophotographic printer or a multifunction machine. In general, an electrophotographic photoreceptor includes a conductive substrate and a photosensitive layer provided directly or indirectly on the conductive substrate. A photoreceptor having a photosensitive layer containing a charge generator, a charge transport agent, and a resin (organic material) that binds these agents is called an electrophotographic organic photoreceptor. Among electrophotographic organophotoreceptors, electrophotographic organophotoreceptors that have a charge transporting function mainly due to containing a charge transporting agent and a charge generating function mainly due to containing a charge generating agent in separate layers are: This is called a multilayer electrophotographic photosensitive member. An electrophotographic organic photoreceptor that includes a charge transporting agent and a charge generating agent in the same layer and that realizes both functions of charge generation and charge transporting in the same layer is referred to as a single-layer electrophotographic photoreceptor.

  On the other hand, an electrophotographic inorganic photosensitive member using an inorganic material (for example, selenium or amorphous silicon photosensitive member) is also exemplified as the photosensitive member. The electrophotographic organic photoreceptor has the advantages that the influence on the environment is relatively small and the film formation and production are easy as compared with the electrophotographic inorganic photoreceptor. Therefore, it is currently used in many image forming apparatuses.

  A tris (4-styrylphenyl) amine derivative is known as a charge transport agent that can be used for an electrophotographic organic photoreceptor (Patent Document 1).

JP 2012-27139 A

  However, even if the derivative described in Patent Document 1 is used as a charge transport agent, an electron having excellent sensitivity characteristics and surface appearance while ensuring solubility of the charge transport agent in a solvent and compatibility with a binder resin. It is difficult to obtain a photographic photoreceptor.

  In view of the above problems, the present invention provides a triarylamine derivative excellent in solubility in a solvent and / or binder resin, and an electrophotographic photoreceptor containing the triarylamine derivative and excellent in sensitivity characteristics and / or surface appearance. To do.

  The triarylamine derivative of the present invention is represented by the following general formula (I).

In the general formula (I),
R ₁ and R ₂ are independently the same or different from each other, and are a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom having 1 substituent which may have a substituent. Selected from the group consisting of an alkoxy group having 6 or less and an aryl group having 6 to 12 carbon atoms, which may have a substituent,
k and l each represents an integer of 0 to 4,
when k represents an integer of 2 or more, a plurality of R ₁ present in the same aromatic ring may be the same or different from each other;
when l represents an integer of 2 or more, a plurality of R ₂ present in the same aromatic ring may be the same or different from each other;
m and n each represent an integer of 1 to 3,
m and n each represent a different integer.

  The electrophotographic photoreceptor of the present invention includes a photosensitive layer. The photosensitive layer is: a stacked photosensitive layer in which a charge generating layer containing a charge generating agent and a charge transporting layer containing a hole transporting agent are laminated, and the charge transporting layer is disposed on the outermost surface; It is a single-layer type photosensitive layer containing a generator and a hole transport agent. The electrophotographic photoreceptor contains the triarylamine derivative as the hole transport agent.

  The triarylamine derivative of the present invention has excellent solubility in a solvent and / or excellent compatibility with a binder resin. By containing the triarylamine derivative of the present invention as a hole transport agent in an electrophotographic photoreceptor, an electrophotographic photoreceptor having excellent sensitivity characteristics and / or excellent surface appearance can be obtained. Such an electrophotographic photoreceptor is considered to be able to form high-quality images over a long period of time.

2 is a ¹ H-NMR spectrum of a triarylamine derivative represented by the formula (HT-2). (A) And (b) is a schematic sectional drawing which respectively shows the structure of the single layer type electrophotographic photoreceptor which concerns on embodiment of this invention. (A) And (b) is a schematic sectional drawing which respectively shows the structure of the laminated electrophotographic photoreceptor which concerns on embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and 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.

[First embodiment: Triarylamine derivative]
The first embodiment of the present invention is a triarylamine derivative. The triarylamine derivative of this embodiment is represented by the following general formula (I).

In general formula (I),
R ₁ and R ₂ are independently the same or different from each other, and are a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom having 1 substituent which may have a substituent. Selected from the group consisting of an alkoxy group having 6 or less and an aryl group having 6 to 12 carbon atoms, which may have a substituent,
k and l each represents an integer of 0 to 4,
when k represents an integer of 2 or more, a plurality of R ₁ present in the same aromatic ring may be the same or different from each other;
when l represents an integer of 2 or more, a plurality of R ₂ present in the same aromatic ring may be the same or different from each other;
m and n each represent an integer of 1 to 3,
m and n each represent a different integer.

  In the triarylamine derivative represented by the general formula (I) (hereinafter sometimes referred to as “triarylamine derivative (I)”), m and n each represent a different integer. That is, among the three substituents introduced into triphenylamine, the structure of one substituent is different from the structures of the other two substituents. The triarylamine derivative (I) having such an asymmetric structure tends to have excellent solubility in a solvent and / or excellent compatibility with a binder resin. Therefore, crystallization of the triarylamine derivative (I) in the photosensitive layer can be suppressed during the formation of the photosensitive layer. As a result, it is possible to effectively obtain an electrophotographic photosensitive member that is difficult to observe a crystallized portion and that has an excellent appearance on the surface of the photosensitive member.

  As described above, the triarylamine derivative (I) is excellent in solubility in a solvent and / or compatibility in a binder resin. Therefore, it is easy to disperse the triarylamine derivative uniformly in the photosensitive layer. A photosensitive layer in which triarylamine derivatives are uniformly dispersed tends to have excellent electrical characteristics (particularly, suppression of residual potential). Thereby, an electrophotographic photoreceptor excellent in sensitivity characteristics can be obtained effectively.

In R ₁ and R ₂ of the general formula (I), the halogen atom is, for example, fluorine, chlorine or bromine.

In R ₁ and R ₂ of the general formula (I), examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, A pentyl group, an isopentyl group, a neopentyl group, or a hexyl group. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

In R ₁ and R ₂ of the general formula (I), an alkoxy group having 1 to 6 carbon atoms is a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or an s-butoxy group. , T-butoxy group, pentyloxy group, isopentyloxy group, neopentyloxy group, or hexyloxy group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group.

In R ₁ and R ₂ of the general formula (I), the aryl group having 6 to 12 carbon atoms is a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, an anthryl group, or a phenanthryl group.

The aforementioned alkyl group, alkoxy group, or aryl group may be substituted with a substituent. Although it does not specifically limit as a substituent, For example, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group is mentioned, for example. Examples of the alkyl group having 1 to 6 carbon atoms as the substituent include the same groups as those exemplified as the alkyl group having 1 to 6 carbon atoms in R ₁ and R ₂ of the general formula (I). Is mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms as the substituent include the same groups as those exemplified as the alkoxy group having 1 to 6 carbon atoms in R ₁ and R ₂ of the general formula (I). Is mentioned. Examples of the aryl group having 6 to 12 carbon atoms as the substituent include the same groups as those exemplified as the aryl group having 6 to 12 carbon atoms in R ₁ and R ₂ of the general formula (I). Is mentioned.

In general formula (I), R ₁ is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms in order to improve solubility in a solvent. Is preferred. R ₂ is preferably an alkoxy group having 1 to 6 carbon atoms for the same reason.

  In general formula (I), it is preferable that k and l each represent an integer of 0 or 1 in order to increase the π-electron conjugation property of the whole molecule. More preferably, l represents an integer of 0.

  It is preferable that k, l, m, and n in the general formula (I) have the following relationship. when each of k and l represents an integer of 0: m represents an integer of 1 and n represents an integer of 2 or 3; or m represents an integer of 2 or 3 and n represents 1 Represents an integer. When at least one of k and l represents an integer of 1 or more, m and n each represent an integer of 1 to 3, and m and n each represent a different integer.

  More preferably, k, l, m, and n in the general formula (I) have the following relationship. When k and l each represent an integer of 0, m represents an integer of 1 and n represents an integer of 2 or 3. When at least one of k and l represents an integer of 1 or more, m and n each represent an integer of 1 to 3, and m and n each represent a different integer.

  More preferably, k, l, m, and n in the general formula (I) have the following relationship. k represents an integer of 0 or 1. l represents an integer of 0. When k represents an integer of 0, m represents an integer of 1 and n represents an integer of 3. When k represents an integer of 1, n is larger than m.

  In the general formula (I), k, l, m, and n preferably have the relationship as described above. Thereby, even if the benzene ring in the substituent which triphenylamine has does not have a substituent (that is, even when k and l each represent an integer of 0), And the difference in the bond structure existing between the phenyl group of the triphenylamine and the benzene ring in the substituent of triphenylamine can be increased. As a result, it is considered that the asymmetry of the structure of the triarylamine derivative (I) is increased and the solubility of the triarylamine derivative (I) in the solvent and / or the compatibility with the binder resin is improved. Such triarylamine derivatives (I) are easily dispersed uniformly in the photosensitive layer. Since the photosensitive layer in which the triarylamine derivative is uniformly dispersed tends to have excellent electrical characteristics (particularly, suppression of residual potential), an electrophotographic photoreceptor excellent in sensitivity characteristics can be obtained. Further, such a triarylamine derivative (I) is hardly crystallized in the photosensitive layer when the photosensitive layer is formed. Therefore, an electrophotographic photosensitive member having an excellent appearance on the surface of the photosensitive member can be obtained.

  Specific examples of the triarylamine derivative (I) are represented by the following structural formulas (HT-1) to (HT-10). Hereinafter, triarylamine derivatives represented by the following structural formulas (HT-1) to (HT-10) may be referred to as triarylamine derivatives (HT-1) to (HT-10), respectively.

Among the specific examples described above, the ¹ H-NMR spectrum of the triarylamine derivative (HT-2) is shown in FIG.

  The triarylamine derivative (I) can be produced according to the following reaction formulas (R-1) to (R-7) or by a method analogous thereto. In addition to the reactions represented by the reaction formulas (R-1) to (R-7), an appropriate step may be included as necessary. Hereinafter, the reactions represented by the reaction formulas (R-1) to (R-7) will be described in detail.

In the reaction formulas (R-1) to (R-5), R has the same meaning as R ₁ or R ₂ in the general formula (I). j is synonymous with k or l in the general formula (I). X represents a halogen atom.

[Reaction Formula (R-1)]
In the reaction formula (R-1), the benzene derivative (1-1) is reacted with triethyl phosphite which is the compound (2) to obtain the phosphonate derivative (3-1).

  The reaction ratio [benzene derivative (1-1): triethyl phosphite] of the benzene derivative (1-1) and the compound (2) triethyl phosphite is 1: 1 to 1: 2 in molar ratio. .5 is preferable. If the number of moles of triethyl phosphite is too small relative to the number of moles of the benzene derivative (1-1), the yield of the phosphonate derivative (3-1) may be excessively lowered. On the other hand, when the number of moles of triethyl phosphite is too large relative to the number of moles of the benzene derivative (1-1), unreacted triethyl phosphite remains excessively after the reaction, and the phosphonate derivative (3-1) Purification may be difficult.

  Regarding the reaction between the benzene derivative (1-1) and triethyl phosphite, the reaction temperature is preferably from 160 ° C. to 200 ° C., and the reaction time is preferably from 2 hours to 10 hours.

[Reaction Formula (R-2)]
In the reaction formula (R-2), the phosphonate derivative (3-1) and the benzaldehyde derivative (4-1) are reacted to obtain the diphenylethene derivative (5-1) (Wittig reaction).

  The reaction ratio of the phosphonate derivative (3-1) to the benzaldehyde derivative (4-1) [phosphonate derivative (3-1): benzaldehyde derivative (4-1)] is 1: 1 to 1: 2. 5 is preferable. If the number of moles of the benzaldehyde derivative (4-1) is too small relative to the number of moles of the phosphonate derivative (3-1), the yield of the diphenylethene derivative (5-1) may be excessively lowered. If the number of moles of the benzaldehyde derivative (4-1) is too large relative to the number of moles of the phosphonate derivative (3-1), the unreacted benzaldehyde derivative (4-1) remains excessively, and the diphenylethene derivative (5- The purification of 1) may be difficult.

  The Wittig reaction can be performed in the presence of a catalyst. Examples of the catalyst used include sodium alkoxide (specifically sodium methoxide or sodium ethoxide), metal hydride (specifically sodium hydride or potassium hydride), or metal salt (specifically Specifically, n-butyllithium) may be mentioned. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  It is preferable that the addition amount of such a catalyst is 1 mol or more and 2 mol or less with respect to 1 mol of benzaldehyde derivative (4-1). If the amount of such a catalyst added is too small, the reactivity may be significantly reduced. On the other hand, if the reaction amount of such a catalyst is excessive, it may be difficult to control the reaction.

  The reaction represented by the reaction formula (R-2) can be carried out 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, Includes benzene or toluene).

  Regarding the reaction between the phosphonate derivative (3-1) and the benzaldehyde derivative (4-1), the reaction temperature is preferably 0 ° C. or more and 50 ° C. or less, and the reaction time is preferably 2 hours or more and 24 hours or less.

[Reaction Formula (R-3)]
In the reaction formula (R-3), the phosphonate derivative (3-1) and the cinnamaldehyde derivative (4-2) are reacted to obtain the diphenylbutadiene derivative (5-2) (Wittig reaction).

  The reaction ratio between the phosphonate derivative (3-1) and the cinnamaldehyde derivative (4-2) [phosphonate derivative (3-1): cinnamaldehyde derivative (4-2)] is 1: 1 to 1: It is preferably 2.5. If the number of moles of the cinnamaldehyde derivative (4-2) is too small relative to the number of moles of the phosphonate derivative (3-1), the yield of the diphenylbutadiene derivative (5-2) may be excessively lowered. If the number of moles of the cinnamaldehyde derivative (4-2) is too large relative to the number of moles of the phosphonate derivative (3-1), the unreacted cinnamaldehyde derivative (4-2) remains excessively, and the diphenylbutadiene derivative ( 5-2) may be difficult to purify.

  The Wittig reaction can be performed in the presence of a catalyst. As a catalyst used, the catalyst illustrated by reaction represented by Reaction formula (R-2) is mentioned, for example. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the catalyst added is preferably 1 mol or more and 2 mol or less with respect to 1 mol of the cinnamaldehyde derivative (4-2). If the amount of such a catalyst added is too small, the reactivity may be significantly reduced. On the other hand, if the reaction amount of such a catalyst is excessive, it may be difficult to control the reaction.

  The reaction represented by the reaction formula (R-3) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction represented by Reaction formula (R-2) is mentioned, for example.

  Regarding the reaction between the phosphonate derivative (3-1) and the cinnamaldehyde derivative (4-2), the reaction temperature is preferably 0 ° C. or more and 50 ° C. or less, and the reaction time is preferably 2 hours or more and 24 hours or less. .

[Reaction Formula (R-4)]
In the reaction formula (R-4), the benzene derivative (1-3) and the compound (2) triethyl phosphite are reacted to obtain the phosphonate derivative (3-3).

  The reaction ratio [benzene derivative (1-3): triethyl phosphite] of the benzene derivative (1-3) and the compound (2) triethyl phosphite is 1: 1 to 1: 2 in molar ratio. .5 is preferable. If the number of moles of triethyl phosphite is too small relative to the number of moles of the benzene derivative (1-3), the yield of the phosphonate derivative (3-3) may be excessively lowered. On the other hand, when the number of moles of triethyl phosphite is too large relative to the number of moles of benzene derivative (1-3), unreacted triethyl phosphite remains excessively after the reaction, and phosphonate derivative (3-3) Purification of the product may be difficult.

  Regarding the reaction between the benzene derivative (1-3) and triethyl phosphite, the reaction temperature is preferably from 160 ° C. to 200 ° C., and the reaction time is preferably from 2 hours to 10 hours.

[Reaction Formula (R-5)]
In the reaction formula (R-5), the phosphonate derivative (3-3) and the cinnamaldehyde derivative (4-3) are reacted to obtain the diphenylhexatriene derivative (5-3) (Wittig reaction).

  The reaction ratio between the phosphonate derivative (3-3) and the cinnamaldehyde derivative (4-3) [phosphonate derivative (3-3): cinnamaldehyde derivative (4-3)] is 1: 1 to 1: It is preferably 2.5. If the number of moles of the cinnamaldehyde derivative (4-3) is too small relative to the number of moles of the phosphonate derivative (3-3), the yield of the diphenylhexatriene derivative (5-3) may be excessively lowered. When the number of moles of the cinnamaldehyde derivative (4-3) is too large relative to the number of moles of the phosphonate derivative (3-3), the unreacted cinnamaldehyde derivative (4-3) remains excessively, and the diphenylhexatriene derivative Purification of (5-3) may be difficult.

  The Wittig reaction can be performed in the presence of a catalyst. As a catalyst used, the catalyst illustrated by reaction represented by Reaction formula (R-2) is mentioned, for example. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the catalyst added is preferably 1 mol or more and 2 mol or less with respect to 1 mol of the cinnamaldehyde derivative (4-3). If the amount of such a catalyst added is too small, the reactivity may be significantly reduced. On the other hand, if the reaction amount of such a catalyst is excessive, it may be difficult to control the reaction.

  The reaction represented by the reaction formula (R-5) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction represented by Reaction formula (R-2) is mentioned, for example.

  Regarding the reaction between the phosphonate derivative (3-3) and the cinnamaldehyde derivative (4-3), the reaction temperature is preferably 0 ° C. or more and 50 ° C. or less, and the reaction time is preferably 2 hours or more and 24 hours or less. .

In reaction formula (R-6) ~ (R -7), R 1, R 2, k, l, m and n each, R ₁ in the general formula _{(I), R 2, k} , l, m and n Is synonymous with X represents a halogen atom.

[Reaction Formula (R-6)]
In the reaction formula (R-6), a diphenylethene derivative (5-1 ″), a diphenylbutadiene derivative (5-2 ″), or a diphenylhexatriene derivative (5-3 ″) is reacted with lithium amide. To obtain an intermediate compound (coupling reaction). Here, the diphenylethene derivative (5-1 ″) is a diphenylethene derivative (5-1) obtained by the above-described reaction, wherein each of R and j is R ₂ and l in the general formula (I). It is a compound that is synonymous. In the diphenylbutadiene derivative (5-2 ″), in the diphenylbutadiene derivative (5-2) obtained by the above reaction, each of R and j is synonymous with R ₂ and l in the general formula (I). A compound. In the diphenylhexatriene derivative (5-3 ″), among the diphenylhexatriene derivative (5-3) obtained by the above reaction, each of R and j is synonymous with R ₂ and l in the general formula (I). It is a compound which is.

  Reaction ratio of diphenylethene derivative (5-1 ″), diphenylbutadiene derivative (5-2 ″), or diphenylhexatriene derivative (5-3 ″) and lithium amide [derivative (5-1 ″) ), (5-2 ″), or (5-3 ″): lithium amide] is preferably in a molar ratio of 5: 1 to 1: 1.

  If the number of moles of lithium amide relative to the number of moles of the derivative (5-1 ″), (5-2 ″), or (5-3 ″) is too small, the yield of the intermediate compound is excessively decreased. Sometimes. On the other hand, if the number of moles of lithium amide relative to the number of moles of the derivative (5-1 ″), (5-2 ″), or (5-3 ″) is too large, unreacted lithium amide is reacted after the reaction. It may remain excessively, making it difficult to purify the intermediate compound.

  Regarding the reaction represented by the reaction formula (R-6), the reaction temperature is preferably 80 ° C. or higher and 140 ° C. or lower, and the reaction time is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction represented by the reaction formula (R-6), it is preferable to use a palladium compound as a catalyst. Thereby, the activation energy in the reaction represented by the reaction formula (R-6) can be reduced. As a result, the yield of the intermediate compound can be further improved.

  Examples of the palladium compound include tetravalent palladium compounds, divalent palladium compounds, and other palladium compounds. Examples of the tetravalent palladium compounds include sodium hexachloropalladium (IV) tetrahydrate or potassium hexachloropalladium (IV) tetrahydrate. Examples of the divalent palladium compounds include palladium chloride (II), palladium bromide (II), palladium acetate (II), palladium acetyl acetate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (triphenyl). Phosphine) 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). . Moreover, 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 0.0005 mol or more and 20 mol or less with respect to 1 mol of the derivative (5-1 ″), (5-2 ″), or (5-3 ″). Preferably, it is 0.001 mol or more and 1 mol or less.

  Such a palladium compound may have a structure including a ligand. Thereby, the reactivity of reaction represented by Reaction formula (R-6) can be improved. Examples of the ligand include tricyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, trifurylphosphine, tri (o-tol) 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 0.0005 mol or more and 20 mol or less with respect to 1 mol of the derivative (5-1 ″), (5-2 ″), or (5-3 ″). It is more preferable that it is 0.001 mol or more and 1 mol or less.

  The reaction represented by the reaction formula (R-6) is preferably performed in the presence of a base. Thereby, the hydrogen halide generated in the reaction system is immediately neutralized, and the catalytic activity can be improved. As a result, the yield of the intermediate compound can be improved.

  The base may be an inorganic base or an organic base. As the organic base, for example, an alkali metal alkoxide (specifically, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, or potassium tert-butoxide) is preferable. Sodium tert-butoxide is more preferred. Examples of the inorganic base include tripotassium phosphate or cesium fluoride.

  When 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1 mol of the derivative (5-1 ″), (5-2 ″), or (5-3 ″), the amount of the base added Is preferably 1 mol or more and 50 mol or less, and more preferably 1 mol or more and 30 mol or less.

  The reaction represented by the reaction formula (R-6) can be carried out in a solvent. Examples of the solvent include xylene (specifically, o-xylene), toluene, tetrahydrofuran, or dimethylformamide.

[Reaction Formula (R-7)]
In the reaction formula (R-7), a diphenylethene derivative (5-1 ′), a diphenylbutadiene derivative (5-2 ′), or a diphenylhexatriene derivative (5-3 ′) and the obtained intermediate compound are obtained. The reaction is carried out to obtain the target compound triarylamine derivative (I) (coupling reaction). Here, the diphenylethene derivative (5-1 ′) is the same as R ₁ and k in the general formula (I) in which R and j are the same among the diphenylethene derivative (5-1) obtained by the above reaction. It is a compound which is. The diphenylbutadiene derivative (5-2 ′) is a compound in which R and j are the same as R ₁ and k in the general formula (I) among the diphenylbutadiene derivatives (5-2) obtained by the above-described reaction. It is. In the diphenylhexatriene derivative (5-3 ′), among the diphenylhexatriene derivative (5-3) obtained by the above reaction, each of R and j has the same meaning as R ₁ and k in formula (I). It is a certain compound.

  Reaction ratio between the diphenylethene derivative (5-1 ′), diphenylbutadiene derivative (5-2 ′), or diphenylhexatriene derivative (5-3 ′) and the intermediate compound [derivative (5-1 ′), ( 5-2 ′) or (5-3 ′): intermediate compound] is preferably in a molar ratio of 5: 1 to 1: 1.

  When the number of moles of the intermediate compound relative to the number of moles of the derivative (5-1 ′), (5-2 ′), or (5-3 ′) is too small, the yield of the triarylamine derivative (I) is excessively increased. May decrease. On the other hand, if the number of moles of the intermediate compound relative to the number of moles of the derivative (5-1 ′), (5-2 ′), or (5-3 ′) is too large, the unreacted intermediate compound is excessively increased after the reaction. It may remain and it may be difficult to purify the triarylamine derivative (I).

  Regarding the reaction represented by the reaction formula (R-7), the reaction temperature is preferably 80 ° C. or higher and 140 ° C. or lower, and the reaction time is preferably 2 hours or longer and 10 hours or shorter.

  In the reaction represented by the reaction formula (R-7), a palladium compound is preferably used as a catalyst. Thereby, the activation energy in the reaction represented by the reaction formula (R-7) can be reduced. As a result, the yield of the triarylamine derivative (I) can be further improved.

  As a palladium compound, the palladium compound illustrated by reaction represented by Reaction formula (R-6) is mentioned, for example. 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 with respect to 1 mol of the derivative (5-1 ′), (5-2 ′), or (5-3 ′). Preferably they are 0.001 mol or more and 1 mol or less.

  Such a palladium catalyst may have a structure including a ligand. Thereby, the reactivity of reaction represented by Reaction formula (R-7) can be improved. As a ligand, the ligand illustrated by reaction represented by Reaction formula (R-6) is mentioned, for example. 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 with respect to 1 mol of the derivative (5-1 ′), (5-2 ′), or (5-3 ′), More preferably, it is 0.001 mol or more and 1 mol or less.

  The reaction represented by the reaction formula (R-7) is preferably performed in the presence of a base. Thereby, the hydrogen halide generated in the reaction system is immediately neutralized, and the catalytic activity can be improved. As a result, the yield of the triarylamine derivative (I) can be improved.

  The base may be an inorganic base or an organic base. As an organic base and an inorganic base, the organic base and inorganic base which are illustrated with Reaction formula (R-6) are mentioned, for example.

  When 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1 mol of the derivative (5-1 ′), (5-2 ′), or (5-3 ′), the addition amount of the base is 1 It is preferably at least 1 mol and not more than 10 mol, more preferably at least 1 mol and not more than 5 mol.

  The reaction represented by the reaction formula (R-7) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction represented by Reaction formula (R-6) is mentioned, for example.

[Second Embodiment: Electrophotographic Photoreceptor]
The second embodiment of the present invention is an electrophotographic photoreceptor (hereinafter sometimes simply referred to as “photoreceptor”). The electrophotographic photoreceptor of this embodiment includes a photosensitive layer. The photosensitive layer is a laminated type photosensitive layer or a single layer type photosensitive layer.

  The electrophotographic photoreceptor of this embodiment may be a so-called laminated electrophotographic photoreceptor having a laminated photosensitive layer. The laminated photosensitive layer includes at least a charge generation layer and a charge transport layer, and has a configuration in which the charge transport layer is disposed on the outermost surface. The charge generation layer contains at least a charge generation agent. The charge transport layer contains at least a hole transport agent.

  Further, the electrophotographic photosensitive member of this embodiment may be a so-called single layer type electrophotographic photosensitive member having a single layer type photosensitive layer. The single-layer type photosensitive layer contains at least a charge generator and a hole transport agent in the same layer.

<Single layer type electrophotographic photoreceptor>
Hereinafter, a single layer type electrophotographic photosensitive member having a single layer type photosensitive layer will be described with reference to FIG. As shown in FIG. 2A, the single layer type electrophotographic photoreceptor 20 includes a base 21 and a single layer type photosensitive layer 22. The single layer type photosensitive layer 22 is provided on the substrate 21. The single-layer type photosensitive layer 22 contains a charge generator and a charge transport agent, and may contain a binder resin as necessary. The charge transfer agent is preferably a hole transfer agent or an electron transfer agent.

  The single layer type electrophotographic photosensitive member 20 is not particularly limited as long as it includes a base 21 and a single layer type photosensitive layer 22. For example, as shown in FIG. 2A, a single-layer type photosensitive layer 22 may be directly provided on the substrate 21. Alternatively, as shown in FIG. 2B, an intermediate layer 23 may be provided between the base 21 and the single-layer type photosensitive layer 22.

  The thickness of the single-layer type photosensitive layer 22 is not particularly limited as long as the function as the photosensitive layer can be sufficiently expressed. Specifically, the thickness of the single-layer type photosensitive layer 22 is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less.

<Laminated electrophotographic photoreceptor>
Hereinafter, with reference to FIG. 3, a multilayer electrophotographic photosensitive member having a multilayer photosensitive layer will be described. As shown in FIG. 3A, the multilayer electrophotographic photoreceptor 10 includes a multilayer photosensitive layer 12 on a substrate 11. On the multilayer photosensitive layer 12, a charge generation layer 13 and a charge transport layer 14 are laminated in the order described. By providing the charge transport layer 14 on the outermost surface, it becomes easy to improve wear resistance while maintaining excellent electrical characteristics.

  The charge generation layer 13 contains a charge generation agent. The charge transport layer 14 contains a charge transport agent, and may contain a binder resin as necessary. The charge transport agent may be only a hole transport agent, or a hole transport agent and an electron acceptor compound may be used in combination as necessary.

  The multilayer electrophotographic photosensitive member 10 is not particularly limited as long as it includes the substrate 11 and the multilayer photosensitive layer 12. As shown in FIG. 3B, an intermediate layer 15 may be provided between the substrate 11 and the laminated photosensitive layer 12.

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

  In order to prevent the occurrence of image flow and reduce the manufacturing cost, in the electrophotographic photosensitive member (single-layer type electrophotographic photosensitive member and multilayer electrophotographic photosensitive member) according to the present embodiment, a photosensitive layer (single-layer type photosensitive member). Layer and laminated photosensitive layer) are preferably arranged as outermost layers.

<Common components>
Hereinafter, the elements constituting the single layer type electrophotographic photosensitive member and the multilayer type electrophotographic photosensitive member will be described in detail.

[Substrate]
In the present embodiment, the substrate is not particularly limited as long as at least the surface portion is a substrate having conductivity. Specifically, the base may be a base made of a conductive material. Alternatively, it may be a substrate having a configuration in which the surface of a plastic material or glass is coated or vapor-deposited with a conductive material. Here, examples of the conductive material include metals such as aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, or brass, Or the alloy of these metals is mentioned. These electrically conductive materials may be used alone or in combination of two or more.

  Of the substrates exemplified as described above, a substrate containing aluminum or an aluminum alloy is preferably used. This is because, when such a substrate is used, the charge transfer from the photosensitive layer to the substrate tends to be good, so that a photoreceptor capable of forming a higher quality image can be provided.

  The shape of the substrate can be selected as appropriate and is not particularly limited. For example, a sheet shape or a drum shape may be used. Further, it is desirable that the substrate has sufficient mechanical strength when used.

[Charge generator]
The charge generator is not particularly limited as long as it is a charge generator for an electrophotographic photoreceptor. Examples of the charge generator include X-type metal-free phthalocyanine (x-H ₂ Pc), Y-type titanyl phthalocyanine (Y-TiOPc), perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal Naphthalocyanine pigments, squaraine pigments, trisazo pigments, indigo pigments, azurenium pigments, cyanine pigments, powders of inorganic photoconductive materials such as selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, pyrylium salts, ansanthrone Pigments, triphenylmethane pigments, selenium pigments, toluidine pigments, pyrazoline pigments, or quinacridone pigments.

A charge generator having an absorption wavelength in a desired region may be used alone, or two or more charge generators may be used in combination. Furthermore, for example, in a digital optical system image forming apparatus (for example, a laser beam printer or facsimile using a light source such as a semiconductor laser), it is preferable to use a photoconductor having sensitivity in a wavelength region of 700 nm or more. Therefore, for example, phthalocyanine pigments such as X-type metal-free phthalocyanine (x-H ₂ Pc) or Y-type titanyl phthalocyanine (Y-TiOPc) are preferably used. The crystal shape of the phthalocyanine pigment is not particularly limited, and phthalocyanine pigments having various crystal shapes are used.

  For 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 about 350 nm to 550 nm), an santhrone pigment or a perylene pigment is suitable as a charge generator. Used for.

  In the multilayer electrophotographic photosensitive member, the content of the charge generating agent is preferably 5 parts by mass or more and 1000 parts by mass or less, and 30 parts by mass or more with respect to 100 parts by mass of the base resin contained in the charge generation layer 13. More preferably, it is 500 parts by mass or less. The base resin will be described later.

  In the single layer type electrophotographic photosensitive member, the content of the charge generator is preferably 0.1 parts by weight or more and 50 parts by weight or less, and 0.5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the binder resin. It is more preferable that the amount is not more than parts.

[Charge transport agent]
In the present embodiment, the photosensitive layer contains a charge transport agent. The charge transport agent is in particular a hole transport agent.

(Hole transport agent)
The hole transport agent used in the electrophotographic photosensitive member of the present embodiment is the triarylamine derivative (I) of the first embodiment.

  In the multilayer electrophotographic photosensitive member, the content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, and 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferable.

  In the single-layer electrophotographic photosensitive member, the content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, and preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.

(Electron transfer agent and electron acceptor compound)
The photosensitive layer may contain an electron transport agent or an electron acceptor compound as necessary. The single layer type photosensitive layer of the single layer type electrophotographic photosensitive member can contain an electron transport agent. Thereby, the single-layer type photosensitive layer can transport electrons, and it is easy to impart bipolar (bipolar) characteristics to the single-layer type photosensitive layer. On the other hand, the laminate type photosensitive layer of the laminate type electrophotographic photoreceptor can contain an electron acceptor compound. Thereby, the hole transport ability of a hole transport agent can be improved.

  Examples of the electron transfer agent or the electron acceptor compound include quinone compounds (specifically, naphthoquinone compounds, diphenoquinone compounds, anthraquinone compounds, azoquinone compounds, nitroanthraquinone compounds, or dinitroanthraquinone compounds), malononitrile. Compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2,4,8-tri Examples include nitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, succinic anhydride, maleic anhydride, or dibromomaleic anhydride. The electron transfer agent or the electron acceptor compound is used alone or in combination of two or more.

  In the multilayer electrophotographic photosensitive member, the content of the electron acceptor compound is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the binder resin. The following is more preferable.

  In the single layer type electrophotographic photoreceptor, the content of the electron transport agent is preferably 5 parts by mass or more and 100 parts by mass or less, and preferably 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferable.

[resin]
(Base resin)
The charge generation layer included in the multilayer photosensitive layer includes a base resin (base resin for charge generation layer).

  The base resin for the charge generation layer is not particularly limited as long as it is a resin for the charge generation layer of the multilayer electrophotographic photosensitive member.

  Usually, in a multilayer electrophotographic photosensitive member, a charge generation layer and a charge transport layer are formed. Therefore, in the multilayer electrophotographic photosensitive member, the base resin for the charge generation layer is preferably a resin different from the binder resin so as not to be dissolved in the solvent used for the coating liquid when forming the charge transport layer. .

  Specific examples of the base resin for charge generation layer include styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, 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, polyurethane resin, polysulfone resin, diallyl phthalate resin, ketone Examples include resins, polyvinyl acetal resins, polyvinyl butyral resins, polyether resins, silicone resins, epoxy resins, phenol resins, urea resins, melamine resins, epoxy acrylate resins, and urethane-acrylate resins. As the base resin for the charge generation layer, polyvinyl butyral is preferably used. The base resin for charge generation layer is used singly or in combination of two or more.

(Binder resin)
The binder resin is used for a single layer type photosensitive layer of a single layer type electrophotographic photosensitive member or a charge transport layer of a multilayer type electrophotographic photosensitive member. Examples of the binder resin include thermoplastic resins (specifically, polycarbonate resins, styrene resins, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers, styrene-acrylic acid copolymers). Polymer, acrylic copolymer, polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, polyamide Resin, polyurethane resin, polyarylate resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, or polyester resin), thermosetting resin (specifically, silicone resin, epoxy resin, phenol resin) Lumpur resins, urea resins, melamine resins, or other crosslinking thermosetting resins), or, in the photocurable resin (particularly, an epoxy acrylate resin, or urethane - acrylate copolymer resin) and the like. These binder resins are used singly or in combination of two or more.

  The molecular weight of the binder resin is preferably 40000 or more, more preferably 40000 or more and 52500 or less in terms of viscosity average molecular weight. When the molecular weight of the binder resin is too low, the wear resistance of the binder resin cannot be sufficiently increased, and the charge transport layer or the single-layer type photosensitive layer is easily worn. Also, if the molecular weight of the binder resin is too high, the binder resin is difficult to dissolve in a solvent during the formation of the charge transport layer or single layer type photosensitive layer, and the charge transport layer or single layer type photosensitive layer tends to be difficult to form. There is.

[Additive]
In the electrophotographic photoreceptor according to the exemplary embodiment, at least one of a laminated photosensitive layer (specifically, a charge generation layer and a charge transport layer), a single-layer photosensitive layer, and an intermediate layer is an electrophotographic. Various additives may be contained as long as the properties are not adversely affected. Additives include, for example, deterioration inhibitors (specifically, antioxidants, radical scavengers, singlet quenchers, or ultraviolet absorbers), softeners, surface modifiers, extenders, thickeners. , Dispersion stabilizers, waxes, acceptors, donors, surfactants, plasticizers, sensitizers, or leveling agents. Examples of the antioxidant include BHT (di (tert-butyl) p-cresol), hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidinone, or derivatives thereof, organic sulfur compounds, Or an organic phosphorus compound is mentioned.

[Middle layer]
The electrophotographic photoreceptor according to the exemplary embodiment may have an intermediate layer (for example, an undercoat layer). In the single layer type electrophotographic photosensitive member, the intermediate layer is located between the substrate and the single layer type photosensitive layer. In the multilayer electrophotographic photosensitive member, the intermediate layer is interposed between the substrate and the charge generation layer. An intermediate | middle layer contains the resin (resin for intermediate | middle layers) used for an inorganic particle and an intermediate | middle layer, for example. When the intermediate layer is interposed, an increase in resistance can be suppressed by smoothing the flow of current generated when the electrophotographic photosensitive member is exposed while maintaining an insulating state capable of suppressing leakage.

  Examples of the inorganic particles include metal (specifically, aluminum, iron, or copper), metal oxide (specifically, titanium oxide, alumina, zirconium oxide, tin oxide, or zinc oxide), or Non-metal oxide (specifically, silica) particles can be used. These inorganic particles are used alone or in combination of two or more.

  The intermediate layer resin is not particularly limited as long as it is a resin for forming the intermediate layer.

<Method for producing electrophotographic photoreceptor>
A method for producing a single layer type electrophotographic photoreceptor will be described. The single layer type electrophotographic photosensitive member is manufactured by applying a coating solution for a single layer type photosensitive layer (first coating solution) on a substrate and drying it. The first coating liquid is produced by dissolving or dispersing a charge generating agent, a hole transporting agent, a binder resin and, if necessary, an electron transporting agent or various additives in a solvent.

  A method for producing a multilayer electrophotographic photoreceptor will be described. Specifically, first, a charge generation layer coating solution (second coating solution) and a charge transport layer coating solution (third coating solution) are prepared. A charge generation layer is formed by applying the second coating liquid onto the substrate and drying it by an appropriate method. Thereafter, a third coating solution is applied to the charge generation layer and dried to form a charge transport layer, whereby a multilayer electrophotographic photoreceptor can be produced.

  The second coating liquid is prepared by dissolving or dispersing a charge generator, a base resin, and various additives as required in a solvent. The third coating solution is prepared by dissolving or dispersing a hole transport agent, a binder resin and, if necessary, silica particles, an electron acceptor compound or various additives in a solvent.

  The solvent contained in the coating solution (first coating solution, second coating solution, or third coating solution) is not particularly limited as long as each component contained in the coating solution can be dissolved or dispersed. Specifically, examples of the solvent include alcohols (for example, methanol, ethanol, isopropanol, or butanol), aliphatic hydrocarbons (for example, n-hexane, octane, or cyclohexane), and aromatic hydrocarbons (for example, 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), dimethylform Aldehyde, dimethyl formamide, or dimethyl sulfoxide and the like. These solvents are used alone or in combination of two or more. In order to improve the safety and health of workers in the process of manufacturing the photoreceptor, it is preferable to use a non-halogen solvent 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 liquid may contain, for example, a surfactant in order to improve the dispersibility of each component.

  The method for applying the coating solution is not particularly limited as long as the coating solution can be uniformly applied onto the substrate. 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 is not particularly limited as long as the method can evaporate the solvent in the coating solution. 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.

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

(1) Synthesis of triarylamine derivative [synthesis of triarylamine derivative (HT-1)]
A triarylamine derivative (HT-1) was synthesized according to the following reaction scheme. Hereinafter, the reaction scheme will be specifically described.

(Synthesis of Compound (3a))
Compound (1a) (16.1 g, 0.1 mol) and triethyl phosphite (25 g, 0.15 mol) as compound (2) were added to a 200 mL flask, and the mixture was stirred at 180 ° C. for 8 hours. And cooled to room temperature. Thereafter, excess triethyl phosphite was distilled off under reduced pressure to obtain compound (3a) (yield: 24.1 g, yield: 92 mol%) as a white liquid.

(Synthesis of Compound (5a))
The obtained compound (3a) (13 g, 0.05 mol) was added to a 500 mL two-necked flask at 0 ° C. The inside of the flask was replaced with argon gas. Thereafter, dry tetrahydrofuran (100 mL) and 28% sodium methoxide (9.3 g, 0.05 mol) were added to the flask and stirred for 30 minutes. Thereafter, compound (4a) (7 g, 0.05 mol) in dry tetrahydrofuran (300 mL) was added, and the mixture was stirred at room temperature for 12 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 purified with toluene / methanol (20 mL / 100 mL) to obtain compound (5a) (yield: 9.8 g, yield: 80 mol%) as white crystals.

(Synthesis of Compound (5h))
The obtained compound (3a) (13 g, 0.05 mol) was added to a 500 mL two-necked flask at 0 ° C. The inside of the flask was replaced with argon gas. Thereafter, dry tetrahydrofuran (100 mL) and 28% sodium methoxide (9.3 g, 0.05 mol) were added to the flask and stirred for 30 minutes. Thereafter, compound (4h) (5 g, 0.05 mol) in dry tetrahydrofuran (300 mL) was added, and the mixture was stirred at room temperature for 12 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 purified with toluene / methanol (20 mL / 100 mL) to obtain compound (5h) (yield: 8.8 g, yield: 87 mol%) as white crystals.

(Synthesis of Intermediate Compound of Triarylamine Derivative (HT-1))
In a three-necked flask, the obtained compound (5a) (6 g, 0.02 mol), tricyclohexylphosphine (0.0662 g, 0.000189 mol), tris (dibenzylideneacetone) dipalladium (0) (0.0864 g,. 0000944 mol), sodium tert-butoxide (4 g, 0.42 mol), lithium amide (0.24 g, 0.010 mol), and distilled о-xylene (500 mL) were added. The inside of the flask was replaced with argon gas. Thereafter, the contents were stirred at 120 ° C. for 5 hours and cooled to room temperature. The obtained mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, followed by drying treatment and adsorption treatment. Thereafter, the obtained organic layer was distilled off under reduced pressure to remove о-xylene. The obtained residue was crystallized from chloroform / hexane (volume ratio 1: 1) to obtain an intermediate compound (yield: 2.6 g) of the triarylamine derivative (HT-1).

(Synthesis of Triarylamine Derivative (HT-1))
In a three-necked flask, the obtained intermediate compound (2.6 g, 0.006 mol), compound (5h) (1.5 g, 0.006 mol), tricyclohexylphosphine (0.020604 g, 5.887 × 10 ⁻⁵ mol). ), Tris (dibenzylideneacetone) dipalladium (0) (0.026933 g, 2.943 × 10 ⁻⁵ mol), sodium tert-butoxide (1 g, 0.010 mol), and distilled о-xylene (200 mL). added. The inside of the flask was replaced with argon gas. Thereafter, the contents were stirred at 120 ° C. for 5 hours and cooled to room temperature. The obtained mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, followed by drying treatment and adsorption treatment. Thereafter, the obtained organic layer was distilled off under reduced pressure to remove о-xylene. The obtained residue was purified by silica gel column chromatography using chloroform / hexane (volume ratio 1: 1) as a developing solvent, and triarylamine derivative (HT-1) (yield: 3.8 g, yield: 63 mol%) was obtained.

[Synthesis of Triarylamine Derivative (HT-2)]
The following compound (5b) (yield: 85 mol%) was obtained in the same manner as the synthesis of the compound (5h) except that the following compound (4b) was used instead of the compound (4h). Subsequently, the intermediate compound was obtained by the method similar to the synthesis | combination of the intermediate compound of a triarylamine derivative (HT-1). Subsequently, the triarylamine derivative (HT-2) (yield: 65) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5b) was used instead of the compound (5h). Mol%).

The obtained triarylamine derivative (HT-2) was measured using a 300 MHz ¹ H-NMR (proton nuclear magnetic resonance) spectrometer. CDCl ₃ was used as the solvent. ¹ H-NMR spectrum confirmed that a triarylamine derivative (HT-2) was obtained. The ¹ H-NMR spectrum of the triarylamine derivative (HT-2) is shown in FIG.

[Synthesis of Triarylamine Derivative (HT-3)]
The following compound (5c) was synthesized in the same manner as the synthesis of compound (5a) except that the following compound (3b) was used instead of the compound (3a) and the following compound (4c) was used instead of the compound (4a). (Yield: 40 mol%) was obtained. Next, an intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5c) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-3) (yield: 55) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5a) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-4)]
The intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of the triarylamine derivative (HT-1). Subsequently, the triarylamine derivative (HT-4) (yield: 55) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5c) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-5)]
An intermediate compound was obtained by the same method as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5b) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-5) (yield: 60) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5c) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-6)]
An intermediate compound was obtained by the same method as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5b) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-6) (yield: 70) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5a) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-7)]
An intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of triarylamine derivative (HT-1) except that compound (5c) was used instead of compound (5a). Subsequently, the triarylamine derivative (HT-7) (yield: 57) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5b) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-8)]
The following compound (5g) (yield: 75 mol%) was obtained in the same manner as the synthesis of the compound (5a) except that the following compound (4g) was used instead of the compound (4a). Next, an intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5c) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-8) (yield: in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the following compound (5g) was used instead of the compound (5h). 54 mol%) was obtained.

[Synthesis of Triarylamine Derivative (HT-9)]
The following compound (5e) (yield: 70 mol%) was obtained in the same manner as the synthesis of the compound (5a) except that the following compound (4e) was used instead of the compound (4a). Next, an intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5c) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-9) (yield: 55) was obtained in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5e) was used instead of the compound (5h). Mol%).

[Synthesis of Triarylamine Derivative (HT-10)]
The following compound (5f) (yield: 65 mol%) was obtained in the same manner as the synthesis of the compound (5h) except that the following compound (4f) was used instead of the compound (4h). Next, an intermediate compound was obtained in the same manner as the synthesis of the intermediate compound of the triarylamine derivative (HT-1) except that the compound (5f) was used instead of the compound (5a). Subsequently, the triarylamine derivative (HT-10) (yield: 60) was prepared in the same manner as the synthesis of the triarylamine derivative (HT-1) except that the compound (5a) was used instead of the compound (5h). Mol%).

(2) Production of laminated electrophotographic photoreceptor [photosensitive body (A-1)]
Hereinafter, the production of the photoreceptor (A-1) which is a multilayer electrophotographic photoreceptor will be described.

(Formation of intermediate layer)
First, a surface-treated titanium oxide (manufactured by Teika Co., Ltd., “Prototype SMT-02”, number average primary particle size 10 nm) was prepared. Specifically, titanium oxide was surface-treated with alumina and silica, and further surface-treated with methyl hydrogen polysiloxane while wet-dispersing the surface-treated titanium oxide. Next, the surface-treated titanium oxide (2.8 parts by mass) and the copolymerized polyamide resin (manufactured by Daicel Evonik Co., Ltd., “Diamid X4685”) (1 part by mass) were combined with ethanol (10 parts by mass) and butanol ( 2 parts by mass) was added to the solvent. Subsequently, these were mixed for 5 hours using the bead mill, the material was disperse | distributed in the solvent, and the coating liquid for intermediate | middle layers was prepared.

  The obtained intermediate layer coating solution was filtered using a filter having an opening of 5 μm. Then, the coating solution for intermediate | middle layers was apply | coated to the surface of the aluminum drum-shaped support body (diameter 30mm, full length 238.5mm) as a base | substrate using the dip coating method. Subsequently, the applied coating solution was dried at 130 ° C. for 30 minutes to form an intermediate layer (film thickness: 1.5 μm) on the substrate (drum-like support).

(Formation of charge generation layer)
Y-type titanyl phthalocyanine (1 part by mass) as a charge generating agent and polyvinyl butyral resin (manufactured by Denki Kagaku Kogyo Co., Ltd., “Denka Butyral # 6000EP”) (1 part by mass) as a base resin are mixed with propylene glycol monomethyl ether It added with respect to the solvent containing (40 mass parts) and tetrahydrofuran (40 mass parts). Subsequently, these were mixed for 2 hours using the bead mill, the material was disperse | distributed in the solvent, and the 2nd coating liquid was produced. The obtained second coating liquid was filtered using a filter having an opening of 3 μm. Next, the obtained filtrate was applied on the intermediate layer formed as described above using a dip coating method and dried at 50 ° C. for 5 minutes. As a result, a charge generation layer (thickness: 0.3 μm) was formed on the intermediate layer.

(Formation of charge transport layer)
Triarylamine derivative (HT-1) (70 parts by mass) as a hole transport agent, BHT (di (tert-butyl) p-cresol) (5 parts by mass) as an antioxidant, and binder resin Z-type polycarbonate resin (manufactured by Teijin Chemicals Ltd., “TS2050, viscosity average molecular weight 50000”) (100 parts by mass) was added to a solvent containing tetrahydrofuran (430 parts by mass) and toluene (430 parts by mass). This was mixed for 12 hours using a circulating ultrasonic dispersion device, and each component was dispersed in a solvent to prepare a third coating solution.

  The third coating solution was applied on the charge generation layer formed as described above by the same operation as that of the second coating solution. Thereafter, the film was dried at 130 ° C. for 30 minutes to form a charge transport layer (film thickness 20 μm) on the charge generation layer. As a result, a photoreceptor (A-1) which is a multilayer electrophotographic photoreceptor was obtained. In the photoreceptor (A-1), the intermediate layer, the charge generation layer, and the charge transport layer were laminated on the base in the order described.

[Photoreceptor (A-2)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-2) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-2) was produced.

[Photoreceptor (A-3)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-3) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-3) was produced.

[Photoreceptor (A-4)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-4) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-4) was produced.

[Photoreceptor (A-5)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-5) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-5) was produced.

[Photosensitive member (A-6)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-6) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-6) was produced.

[Photosensitive member (A-7)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-7) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-7) was produced.

[Photoreceptor (A-8)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-8) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-8) was produced.

[Photosensitive member (A-9)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-9) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-9) was produced.

[Photosensitive member (A-10)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triarylamine derivative (HT-10) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (A-10) was produced.

[Photoreceptor (B-1)]
Photosensitivity is obtained in the same manner as in the production of the photoreceptor (A-1) except that the following triarylamine derivative (HT-A) is used instead of the triarylamine derivative (HT-1) as the hole transport agent. Body (B-1) was produced.

[Photoreceptor (B-2)]
Photosensitivity is obtained by the same method as in the production of the photoreceptor (A-1) except that the following triarylamine derivative (HT-B) is used instead of the triarylamine derivative (HT-1) as a hole transport agent. Body (B-2) was produced.

(3) Production of single-layer type electrophotographic photosensitive member [photosensitive member (C-1)]
In the container, an X-type metal-free phthalocyanine (5 parts by mass) as a charge generating agent, a triarylamine derivative (HT-1) (80 parts by mass) as a hole transporting agent, and the following compound as an electron transporting agent (ET-1) (50 parts by mass), polycarbonate resin as a binder resin (trade name “Panlite (registered trademark)”) (100 parts by mass) as a binder resin, and tetrahydrofuran (800 parts by mass) as a solvent ). The contents were mixed for 50 hours with a ball mill, and the material was dispersed in a solvent to obtain a single-layer photosensitive layer coating solution (first coating solution).

  Next, the obtained first coating solution was applied to the surface of an aluminum drum-shaped support (diameter 30 mm, total length 238.5 mm) as a substrate using a dip coating method. Thereafter, heat treatment (hot air drying) was performed at 100 ° C. for 30 minutes to form a single layer type photosensitive layer (film thickness: 25 μm), thereby obtaining a photosensitive member (C-1) which is a single layer type electrophotographic photosensitive member.

[Photosensitive member (C-2)]
The photoconductor (C-2) was prepared in the same manner as in the production of the photoconductor (C-1) except that the following compound (ET-4) was used instead of the compound (ET-1) as the electron transfer agent. Manufactured.

[Photosensitive member (C-3)]
Photosensitive material (C Photoconductor (C-3) was produced in the same manner as in production of -1).

[Photosensitive member (C-4)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-2) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-4) was produced.

[Photoreceptor (C-5)]
A triarylamine derivative (HT-2) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoconductor (C-5) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-6)]
A photoconductor (C-6) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-2) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-7)]
The photoconductor was prepared in the same manner as the photoconductor (C-1) except that the triarylamine derivative (HT-3) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-7) was produced.

[Photosensitive member (C-8)]
A triarylamine derivative (HT-3) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoconductor (C-8) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-9)]
A photoconductor (C-9) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-3) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-10)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-4) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-10) was produced.

[Photosensitive member (C-11)]
A triarylamine derivative (HT-4) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoconductor (C-11) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-12)]
A photoconductor (C-12) was produced in the same manner as in the production of the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-4) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-13)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-5) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-13) was produced.

[Photosensitive member (C-14)]
A triarylamine derivative (HT-5) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoreceptor (C-14) was produced in the same manner as in the production of the photoreceptor (C-1) except that was used.

[Photosensitive member (C-15)]
A photoconductor (C-15) was produced by the same method as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-5) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-16)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-6) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-16) was produced.

[Photosensitive member (C-17)]
Triarylamine derivative (HT-6) is used instead of triarylamine derivative (HT-1) as a hole transport agent, and compound (ET-4) is used instead of compound (ET-1) as an electron transport agent. A photoconductor (C-17) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-18)]
A photoconductor (C-18) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-6) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-19)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-7) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-19) was produced.

[Photosensitive member (C-20)]
Triarylamine derivative (HT-7) is used instead of triarylamine derivative (HT-1) as a hole transport agent, and compound (ET-4) is used instead of compound (ET-1) as an electron transport agent. A photoconductor (C-20) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-21)]
A photoconductor (C-21) was produced in the same manner as in the production of the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-7) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-22)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-8) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-22) was produced.

[Photosensitive member (C-23)]
Triarylamine derivative (HT-8) is used instead of triarylamine derivative (HT-1) as a hole transport agent, and compound (ET-4) is used instead of compound (ET-1) as an electron transport agent. A photoreceptor (C-23) was produced in the same manner as in the production of the photoreceptor (C-1) except that was used.

[Photosensitive member (C-24)]
A photoconductor (C-24) was produced by the same method as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-8) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (C-25)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-9) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (C-25) was produced.

[Photosensitive member (C-26)]
A triarylamine derivative (HT-9) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoreceptor (C-26) was produced in the same manner as in the production of the photoreceptor (C-1) except that was used.

[Photosensitive member (C-27)]
A photoconductor (C-27) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-9) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photoreceptor (C-28)]
A photoconductor in the same manner as in the production of the photoconductor (C-1) except that a triarylamine derivative (HT-10) was used instead of the triarylamine derivative (HT-1) as a hole transport agent. (C-28) was produced.

[Photosensitive member (C-29)]
A triarylamine derivative (HT-10) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoconductor (C-29) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (C-30)]
A photoconductor (C-30) was produced in the same manner as in the production of the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-10) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (D-1)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-A) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (D-1) was produced.

[Photosensitive member (D-2)]
A triarylamine derivative (HT-A) is used instead of the triarylamine derivative (HT-1) as a hole transport agent, and a compound (ET-4) is used instead of the compound (ET-1) as an electron transport agent. A photoconductor (D-2) was produced in the same manner as the photoconductor (C-1) except that was used.

[Photosensitive member (D-3)]
A photoconductor (D-3) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-A) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

[Photosensitive member (D-4)]
A photoconductor in the same manner as in the production of the photoconductor (C-1) except that the triarylamine derivative (HT-B) was used instead of the triarylamine derivative (HT-1) as the hole transport agent. (D-4) was produced.

[Photosensitive member (D-5)]
Triarylamine derivative (HT-B) is used instead of triarylamine derivative (HT-1) as a hole transport agent, and compound (ET-4) is used instead of compound (ET-1) as an electron transport agent. A photoconductor (D-5) was produced in the same manner as in the production of the photoconductor (C-1) except that was used.

[Photosensitive member (D-6)]
A photoconductor (D-6) was produced in the same manner as the photoconductor (C-1) except that the following points were changed. As a charge generating agent, Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine. As the hole transport agent, a triarylamine derivative (HT-B) was used instead of the triarylamine derivative (HT-1). As the electron transporting agent, compound (ET-4) was used instead of compound (ET-1).

  The following evaluation was performed on any of the photoreceptors obtained as described above.

(4) Evaluation of electrical characteristics of multi-layer electrophotographic photosensitive member One of the photosensitive members (A-1) to (A-10) and (B-1) to (B-2) is replaced with a drum sensitivity tester ( (Gentec Co., Ltd.) was used, and it was charged so as to be −700 V at a rotation speed of 31 rpm. Next, monochromatic light (wavelength: 780 nm, half-value width: 20 nm, light intensity: 0.4 μJ / cm ² ) is taken out from the light of the halogen lamp using a bandpass filter, and the monochromatic light thus taken out is laminated type electrophotographic photosensitive member. (Irradiation time: 1.5 seconds). The surface potential was measured when 0.5 seconds had elapsed from the end of irradiation. The measured surface potential was defined as the residual potential (V _L ). The measurement environment was a temperature of 23 ° C. and a humidity of 50% RH.

(5) Evaluation of electrical characteristics of single layer type electrophotographic photosensitive member One of the photosensitive members (C-1) to (C-30) and (D-1) to (D-6) is replaced with a drum sensitivity tester (Gen (Technical Co., Ltd.) was used to charge to +700 V and the potential was measured. The measured potential was taken as the initial surface potential (V _o ). Next, monochromatic light (wavelength: 780 nm, half width: 20 nm, light intensity: 1.5 μJ / cm ² ) is taken out from the light of the halogen lamp using a band pass filter, and the taken out monochromatic light is monolayer type electrophotographic photosensitive. The surface of the body was irradiated (irradiation time: 1.5 seconds). The surface potential was measured when 0.5 seconds had elapsed from the end of irradiation. The measured surface potential was defined as the residual potential (V _L ). The measurement environment was a temperature of 23 ° C. and a humidity of 50% RH.

(6) Appearance evaluation of electrophotographic photosensitive member Photosensitive members (A-1) to (A-10), photosensitive members (B-1) to (B-2), photosensitive members (C-1) to (C-30) ), The entire surface of any one of the photoreceptors (D-1) to (D-6) was observed using an optical microscope, and the presence or absence of a crystallized portion was confirmed. The appearance was evaluated according to the following criteria.
A (good): no crystallized portion is observed.
○ (Normal): Almost no crystallized portion is observed.
X (Poor): A crystallized portion is observed.

  As for each of the multilayer electrophotographic photoreceptors (A-1) to (A-10) and (B-1) to (B-2), the hole transport agent contained in the charge transport layer and the results of various evaluations Is shown in Table 1. For each of the monolayer type electrophotographic photoreceptors (C-1) to (C-30) and (D-1) to (D-6), the charge generating agent and hole transport contained in the monolayer type photosensitive layer Table 2 shows the results of the agent and the electron transport agent and various evaluations.

  As is clear from Tables 1 and 2, the electrophotographic photoreceptors (A-1) to (A-10) and (C-1) using the triarylamine derivatives (HT-1) to (HT-10). In (C-30), not only the crystallization of the photosensitive layer was suppressed, but also the residual potential in electrical property evaluation tended to be low. Accordingly, an electrophotographic photoreceptor excellent in electrical characteristics while maintaining an excellent surface appearance by containing the triarylamine derivatives (HT-1) to (HT-10) as hole transport agents in the electrophotographic photoreceptor. Can be obtained.

  The triarylamine derivative according to the present invention can be suitably used for an electrophotographic photoreceptor.

DESCRIPTION OF SYMBOLS 10 Laminated type electrophotographic photoreceptor 11 Base body 12 Laminated type photosensitive layer 13 Charge generation layer 14 Charge transport layer 15 Intermediate layer 20 Single layer type electrophotographic photosensitive body 21 Base body 22 Single layer type photosensitive layer 23 Intermediate layer

Claims (9)

An electrophotographic photoreceptor having a photosensitive layer,
The photosensitive layer is
It is a single layer type photosensitive layer containing a charge generating agent and a hole transporting agent,
The electrophotographic photoreceptor, wherein the hole transport agent is a triarylamine derivative represented by the following general formula (I).

In the general formula (I),
R ₁ and R ₂ are independently the same or different from each other, and are a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom having 1 substituent which may have a substituent. Selected from the group consisting of an alkoxy group having 6 or less and an aryl group having 6 to 12 carbon atoms, which may have a substituent,
k and l each represents an integer of 0 to 4,
when k represents an integer of 2 or more, a plurality of R ₁ present in the same aromatic ring may be the same or different from each other;
when l represents an integer of 2 or more, a plurality of R ₂ present in the same aromatic ring may be the same or different from each other;
m and n each represent an integer of 1 to 3,
m and n are, respectively, different integer and tables,
When m represents 1, n does not represent 2,
When m represents 2, n does not represent 3,
When m represents 3, n does not represent 2 . In the general formula (I),
R ₁ is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms,
R ₂ is an alkoxy group having 1 to 6 carbon atoms,
The electrophotographic photosensitive member according to claim 1, wherein k and l each represents an integer of 0 or 1. In the general formula (I),
If each of k and l represents an integer of 0,
m represents an integer of 1 and n represents an integer of 3 , or m represents an integer of 2 or 3, and n represents an integer of 1,
When at least one of k and l represents an integer of 1 or more,
The electrophotographic photosensitive member according to claim 1, wherein m and n each represent an integer of 1 to 3, and m and n each represent a different integer. In the general formula (I),
When k and l each represent an integer of 0,
When m represents an integer of 1 and n represents an integer of 3 , and at least one of k and l represents an integer of 1 or more,
The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein m and n each represent an integer of 1 to 3, and m and n each represent a different integer. In the general formula (I),
k represents an integer of 0 or 1,
l represents an integer of 0;
when k represents an integer of 0, m represents an integer of 1 and n represents an integer of 3,
The electrophotographic photoreceptor according to claim 1, wherein when k represents an integer of 1, n is larger than m. The electrophotography according to claim 1, wherein the triarylamine derivative is represented by a chemical formula (HT-5), a chemical formula (HT-6), a chemical formula (HT-7), or a chemical formula (HT-10). Photoconductor .

The electrophotographic photosensitive member according to claim 6, wherein the triarylamine derivative is represented by the chemical formula (HT-7) . The photosensitive layer further includes a binder resin,
The electrophotographic photosensitive member according to claim 1, wherein the binder resin is a Z-type polycarbonate resin. The electrophotographic photosensitive member according to claim 1, wherein the charge generating agent includes Y-type titanyl phthalocyanine .

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