JP2010163395A - Enamine derivative, and electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an enamine derivative for electrophotographic photoreceptors. <P>SOLUTION: The enamine derivative represented by formula (1) (wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are each a hydrogen atom, alkyl, or aryl) is used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an enamine derivative and an electrophotographic photoreceptor.

  As an electrophotographic photosensitive member used in an image forming apparatus or the like, an electrophotographic photosensitive member having a conductive substrate and a photosensitive layer provided on the conductive substrate is known. The electrophotographic photoreceptor is a photoreceptor in which a hole transporting agent, a charge generating agent, a binder resin and, if necessary, a coating solution in which an electron transporting agent is dissolved in a solvent are coated on a conductive substrate and dried. Manufactured by forming layers.

  As the hole transport agent, an enamine derivative is known. As enamine derivatives, for example, compounds (2-1) to (2-3) shown below are known (Patent Document 1).

  However, although the compounds (2-1) to (2-3) are compounds having high planarity, since the conjugated structure for resonance stabilization is small, the solubility in a solvent and the compatibility with a binder resin are low. poor. Accordingly, the sensitivity as a hole transport agent for an electrophotographic photoreceptor is insufficient, and as a result, the sensitivity of the resulting electrophotographic photoreceptor is also insufficient.

Japanese Patent No. 282618

  Therefore, an object of the present invention is to provide an enamine derivative having high sensitivity as a hole transport agent for an electrophotographic photoreceptor, and having excellent solubility in a solvent and compatibility with a binder resin, and an electron having excellent sensitivity. It is to provide a photographic photoreceptor.

  The enamine derivative of the present invention is a compound represented by the following formula (1).

In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. 20 is an aryl group, and R ³ and R ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  The electrophotographic photoreceptor of the present invention has a conductive substrate and a photoreceptor layer provided on the conductive substrate, and the photoreceptor layer is a layer containing the enamine derivative of the present invention. Features.

The enamine derivative of the present invention has high sensitivity as a hole transport agent for an electrophotographic photoreceptor, and is excellent in solubility in a solvent and compatibility with a binder resin.
The electrophotographic photoreceptor of the present invention is excellent in sensitivity.

It is a schematic sectional drawing which shows an example of a single layer type electrophotographic photoreceptor. It is a schematic sectional drawing which shows the other example of a single layer type electrophotographic photoreceptor. It is a schematic sectional drawing which shows the other example of a single layer type electrophotographic photoreceptor. 1 is a schematic cross-sectional view showing an example of a laminated electrophotographic photoreceptor. It is a schematic sectional drawing which shows the other example of a laminated type electrophotographic photoreceptor. It is a < ¹ > H-NMR chart of a compound (1-2). ^{1 is} a ¹ H-NMR chart of a compound (1-3).

<Enamine derivative>
The enamine derivative of the present invention is a compound represented by the following formula (1). Hereinafter, the compound represented by Formula (1) is referred to as Compound (1). Other compounds are described in the same manner.

R ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms. These alkyl groups and aryl groups may or may not have a substituent.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, and hexyl group.
Examples of the aryl group include phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl, phenanthryl, and aralkyl groups.
R ¹ is preferably a methyl group, an ethyl group, or a phenyl group.

R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. These alkyl groups and aryl groups may or may not have a substituent.
Examples of the alkyl group and aryl group include the alkyl groups and aryl groups exemplified above.
R ² is preferably a hydrogen atom or a methyl group.

R ³ and R ⁴ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. These alkyl groups and aryl groups may or may not have a substituent.
Examples of the alkyl group include the methyl group, the ethyl group, the propyl group, and the butyl group exemplified above.
As an aryl group, the phenyl group illustrated previously, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned.
R ³ and R ⁴ are preferably a methyl group or a phenyl group.

  Examples of compound (1) include compounds (1-1) to (1-6).

Compound (1) is produced, for example, as follows. In the reaction formula, X ¹ and X ² are halogen atoms, and R ^{1 to} R ⁴ are the same as those in the formula (1).

(A) Process:
Compound (3) and triethyl phosphite are reacted to form compound (4), and unreacted triethyl phosphite is distilled off under reduced pressure.

  The reaction ratio (molar ratio) between the compound (3) and triethyl phosphite is preferably 1: 1 to 1: 2.5. If there is too little triethyl phosphite, unreacted compound (3) remains and purification becomes difficult. If there is too much triethyl phosphite, the cost increases. The reaction temperature is preferably 160 to 200 ° C., and the reaction time is preferably 2 to 6 hours. By setting it as this range, a desired reaction can be efficiently carried out with a relatively simple production facility.

(B) Process:
Compound (4) and compound (5) are reacted in a solvent in the presence of a base to give compound (6), and compound (6) is extracted and purified.

The reaction ratio (molar ratio) between the compound (4) and the compound (5) is preferably 1: 1 to 1: 2.5. When there is too little compound (4), the yield of compound (6) will decrease. If the amount of compound (4) is too large, the amount of unreacted compound (4) will increase, and purification of compound (6) may be difficult due to side reactions and the like.
The reaction temperature is preferably -20 to 30 ° C, and the reaction time is preferably 5 to 30 hours. By setting it as this range, a desired reaction can be efficiently carried out with a relatively simple production facility.

  Examples of the base include sodium alkoxides such as sodium methoxide and sodium ethoxide; metal hydrides such as sodium hydride and potassium hydride; metal salts such as n-butyllithium and the like. A base may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the base added is preferably 1 to 1.5 mol with respect to 1 mol of compound (5). If the addition amount of the base is less than 1 mol, the reactivity between the compound (4) and the compound (5) may be significantly reduced. When the addition amount of the base exceeds 1.5 mol, it may be difficult to control the reaction between the compound (4) and the compound (5).

  Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane; aromatic hydrocarbons such as benzene and toluene, and dimethylformamide.

(C) Process:
In the presence of a catalyst or the like, the compound (6) and the compound (7) are reacted in a solvent to obtain the compound (8), and the compound (8) is extracted and purified.

The reaction ratio (molar ratio) between the compound (6) and the compound (7) is preferably 1: 1 to 1: 2.5. When there is too little compound (6), the yield of compound (8) will decrease. When there are too many compounds (6), there will be many unreacted compounds (6) and it will become difficult to refine | purify a compound (8) by side reaction etc.
The reaction temperature is preferably 80 to 140 ° C., and the reaction time is preferably 2 to 10 hours. By setting it as this range, a desired reaction can be efficiently carried out with a relatively simple production facility.

Examples of the catalyst include a palladium catalyst. Examples of the palladium-based catalyst include tris (dibenzylideneacetone) dipalladium (0). A catalyst may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the solvent include xylene.

(D) Process:
In the presence of an acid catalyst, the compound (8) and the compound (9) are reacted in a solvent to obtain the compound (1), and the compound (1) is extracted and purified.

The reaction ratio (molar ratio) between the compound (8) and the compound (9) is preferably 1: 1 to 1: 2.5. If the amount of compound (9) is too small, compound (8) remains and purification becomes difficult. When there are too many compounds (9), it will become a cost increase.
The reaction temperature is preferably 60 to 120 ° C., and the reaction time is preferably 1 to 5 hours. By setting it as this range, a desired reaction can be efficiently carried out with a relatively simple production facility.

Examples of the acid catalyst include p-toluenesulfonic acid, camphorsulfonic acid, pyridinium-p-toluenesulfonic acid and the like.
0.05-10 mass parts is preferable with respect to 100 mass parts of compounds (9), and, as for the addition amount of an acid catalyst, 0.2-4 mass parts is more preferable. When the addition amount of the acid catalyst is less than 0.05 parts by mass, the reactivity between the compound (8) and the compound (9) may be significantly reduced. When the addition amount of the acid catalyst exceeds 10 parts by mass, it may be difficult to control the reaction between the compound (8) and the compound (9).

Examples of the solvent include toluene, xylene, chlorobenzene, butanol, diethylene glycol dimethyl ether and the like.
In the step (d), water is produced as a by-product during the reaction. Since this water hinders the reaction, the produced water is preferably azeotroped with the solvent and removed from the reaction system.

  The compound (1) described above is easy to stabilize resonance while maintaining high flatness by expanding the conjugated structure. Compound (1) has an ether structure. The compound (1) having such a structure is excellent in solubility in a solvent and compatibility with a polar binder resin (for example, polycarbonate resin). Therefore, the compound (1) has high sensitivity as a hole transport agent for an electrophotographic photoreceptor.

<Electrophotographic photoreceptor>
The electrophotographic photosensitive member of the present invention has a conductive substrate and a photosensitive layer provided on the conductive substrate, and the photosensitive layer contains the enamine derivative (compound (1)) of the present invention. An electrophotographic photoreceptor which is a layer to be used.

  Examples of the electrophotographic photosensitive member include (i) a single-layer type electrophotographic photosensitive member and (ii) a laminated type electrophotographic photosensitive member, which can be used for either a positive or negative charging type electrophotographic photosensitive member and has a simple structure. (I) single layer for reasons such as easy manufacture, coating film defects at the time of forming a photoreceptor layer can be effectively suppressed, interface between layers is small, and optical characteristics are easily improved. Type electrophotographic photoreceptors are preferred.

(I) Single layer type electrophotographic photosensitive member:
FIG. 1 is a schematic cross-sectional view showing an example of a single layer type electrophotographic photosensitive member. The single layer type electrophotographic photoreceptor 10 includes a conductive substrate 12 and a photoreceptor layer 14 provided on the conductive substrate 12.
The single-layer type electrophotographic photosensitive member 10 is not limited to that shown in FIG. 1, and a single-layer type electrophotographic photosensitive member is interposed between the conductive substrate 12 and the photosensitive layer 14 as shown in FIG. The barrier layer 16 may be provided within a range that does not impede the characteristics of 10, and a protective layer 18 may be provided on the surface of the photoreceptor layer 14 as shown in FIG. 3.

Examples of the conductive substrate include metals such as iron, aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass; Laminated plastic materials; glass coated with aluminum iodide, tin oxide, indium oxide or the like can be used.
Examples of the shape of the conductive substrate include a sheet shape and a drum shape. The shape of the conductive substrate may be appropriately determined according to the structure of the image forming apparatus.

The thickness of the photoreceptor layer is preferably 5 to 100 μm, and more preferably 10 to 50 μm.
The photoreceptor layer is a layer containing, for example, a hole transport agent, a charge generator, a binder resin, and, if necessary, an electron transport agent.

The photoreceptor layer contains the compound (1) as a hole transport agent.
The photoreceptor layer may contain another hole transport agent. Other hole transporting agents include enamine compounds other than compound (1), oxadiazole compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole, 9 Styryl compounds such as-(4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, Examples thereof include nitrogen-containing cyclic compounds such as indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds, and condensed polycyclic compounds. A hole transport agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the photoreceptor layer contains an electron transport agent, examples of the electron transport agent include quinone derivatives, anthraquinone derivatives, malononitrile derivatives, thiopyran derivatives, trinitrothioxanthone derivatives, 3,4,5,7-tetranitro-9-fluorenone derivatives, Dinitroanthracene derivatives, dinitroacridine derivatives, nitroantharaquinone derivatives, dinitroanthraquinone derivatives, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride Maleic anhydride, dibromomaleic anhydride and the like. An electron transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As the electron transporting agent, a quinone derivative is preferable because it is excellent in electron acceptability and compatibility with a charge generating agent, and an electrophotographic photoreceptor excellent in sensitivity characteristics and durability can be obtained. Examples of quinone derivatives include naphthoquinone derivatives, diphenoquinone derivatives, azoquinone derivatives, and the like.
As the electron transfer agent, compounds (10-1) to (10-3) are particularly preferable.

  Examples of the charge generator include phthalocyanine pigments, perylene pigments, bisazo pigments, diketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaraine pigments, trisazo pigments, indigo pigments, azurenium pigments, cyanine pigments, Organic photoconductors such as pyrylium pigment, ansanthrone pigment, triphenylmethane pigment, selenium pigment, toluidine pigment, pyrazoline pigment, quinacridone pigment; selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, etc. And inorganic photoconductive agents. A charge generating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the charge generating agent, when a hole transporting agent and an electron transporting agent are used in combination, an electrophotographic photosensitive member with more excellent sensitivity characteristics, electrical characteristics, stability and the like can be obtained. Therefore, a metal-free phthalocyanine (τ type or X type), titanyl phthalocyanine (α type or Y type), hydroxygallium phthalocyanine (V type), and one or more selected from the group consisting of chlorogallium phthalocyanine (type II) are preferred.

  Examples of the binder resin include polycarbonate resins such as bisphenol Z type, bisphenol ZC type, bisphenol C type, bisphenol A type, polyarylate resin, 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 Polymers, alkyd resins, polyamide resins, polyurethane resins, polysulfone resins, diallyl phthalate resins, ketone resins, polyvinyl butyral resins, polyether resins, etc .; silicone resins, epoxy resins, phenol resins, Containing resins, thermosetting resins such as melamine resin, epoxy acrylate, urethane - photocurable resins such as acrylate. Binder resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The photoreceptor layer may contain a known additive as long as the electrophotographic characteristics are not adversely affected. Examples of additives include antioxidants, radical scavengers, singlet quenchers, deterioration inhibitors such as ultraviolet absorbers, softeners, plasticizers, surface modifiers, extenders, thickeners, dispersion stabilizers. , Wax, acceptor, donor and the like.
In order to improve the sensitivity of the photoreceptor layer, known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generator.

20-500 mass parts is preferable with respect to 100 mass parts of binder resin, and, as for content of a hole transport agent, 30-200 mass parts is more preferable.
When the electron transport agent is contained, the content of the electron transport agent is preferably 5 to 100 parts by mass and more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the binder resin.
The content of the charge generating agent is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

The photoreceptor layer is formed by, for example, applying a hole transporting agent, a charge generating agent, a binder resin, and, if necessary, a coating solution in which an electron transporting agent is dissolved or dispersed in a solvent on a conductive substrate and drying it. Is formed.
The coating liquid is prepared by dissolving or dispersing each component in a solvent using a roll mill, a ball mill, an attritor, a paint shaker, an ultrasonic disperser or the like. As a coating method, a known method may be used.

Examples of the solvent include alcohols such as methanol, ethanol, isopropanol and butanol; aliphatic hydrocarbons such as n-hexane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; dichloromethane, dichloroethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate and methyl acetate Dimethylformaldehyde, dimethylformamide, dimethyl sulfoxide and the like. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
In order to improve the dispersibility of each component and the smoothness of the surface of the photoreceptor layer, a surfactant, a leveling agent, and the like may be added to the coating solution.

  Since the obtained single layer type electrophotographic photoreceptor contains the compound (1) in the photoreceptor layer, the residual potential is lowered and the sensitivity is high. Furthermore, when an electron transporting agent is contained in the photoreceptor layer, electrons are efficiently exchanged between the charge generating agent and the hole transporting agent, and the sensitivity and the like tend to be more stable.

(Ii) Multilayer electrophotographic photoreceptor:
FIG. 4 is a schematic cross-sectional view showing an example of a laminated electrophotographic photosensitive member. The multilayer electrophotographic photoreceptor 20 includes a conductive substrate 12, a charge generation layer 24 containing a charge generation agent provided on the conductive substrate 12, and a charge transport layer 22 provided on the charge generation layer 24. And have. In the multilayer electrophotographic photoreceptor 20, the charge generation layer 24 and the charge transport layer 22 constitute a photoreceptor layer.

The multilayer electrophotographic photosensitive member 20 is not limited to that shown in FIG. 4, and as shown in FIG. 5, a charge transport layer 22 is provided on the conductive substrate 12, and charge generation is generated on the charge transport layer 22. A layer 24 may be provided. However, since the charge generation layer 24 is thinner than the charge transport layer 22, the charge transport layer 22 is preferably provided on the charge generation layer 24 in order to protect the charge generation layer 24.
Examples of the conductive substrate include those similar to the single-layer type electrophotographic photosensitive member.

The thickness of the charge generation layer is preferably from 0.01 to 5 μm, and more preferably from 0.1 to 3 μm.
The thickness of the charge transport layer is preferably 2 to 100 μm, and more preferably 5 to 50 μm.
Depending on the order of formation of the charge generation layer and the charge transport layer, and the type of charge transport agent used in the charge transport layer, the laminate type electrophotographic photoreceptor is selected as a positive or negative charge type. For example, in a laminated electrophotographic photosensitive member in which a charge generation layer is provided on a conductive substrate and a charge transport layer is provided thereon, a hole transport agent such as compound (1) is used as a charge transport agent for the charge transport layer. When used, the photoreceptor is of a negative charge type. In this case, the charge generation layer may contain an electron transport agent.

Examples of the charge generating agent, hole transporting agent, electron transporting agent, and binder are the same as those for the single-layer type electrophotographic photosensitive member.
The content of the charge generation agent in the charge generation layer is preferably 5 to 1000 parts by mass, more preferably 30 to 500 parts by mass with respect to 100 parts by mass of the binder resin.
When the hole transport agent is contained in the charge generation layer, the content of the hole transport agent is preferably 10 to 500 parts by weight, and more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the binder resin.

10-500 mass parts is preferable with respect to 100 mass parts of binder resin, and, as for content of the hole transport agent of a charge transport layer, 25-200 mass parts is more preferable.
When the electron transport agent is contained in the charge transport layer, the content of the electron transport agent is preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the binder resin.

The charge generation layer is formed, for example, by means such as vapor deposition or coating.
The charge transport layer is formed by means such as coating as in the case of the photoreceptor layer of a single-layer electrophotographic photoreceptor.

  Thus, since the electrophotographic photoreceptor of the present invention has a photoreceptor layer containing a specific enamine derivative (compound (1)), it is excellent in sensitivity.

Each evaluation in the examples was performed as follows.
(Electrical characteristics test)
Established the single-layer type electrophotographic photoconductor in GENTEC Co. drum sensitivity tester was so charges the single-layer type electrophotographic photoreceptor comprising an initial surface potential V ₀ which is + 700 V. Next, monochromatic light (light intensity 1.5 μJ / cm ² ) having a wavelength of 780 nm (half-value width 20 nm) extracted from the white light of the halogen lamp using a bandpass filter is applied to the surface of the single-layer electrophotographic photosensitive member. The surface potential was measured after 0.5 seconds from the start of exposure, and this was defined as the residual potential V _L (V).

(Appearance evaluation)
The surface of the photoreceptor layer of the single layer type electrophotographic photoreceptor was observed. The case where no crystallization was observed was evaluated as ◯, the case where it was slightly crystallized was evaluated as Δ, and the case where it was crystallized was evaluated as ×.

[Production of Compound (1-1)]
(A) Process:
A 200 mL flask was charged with 15.2 g (0.10 mol) of the compound (3-1) and 25 g (0.15 mol) of triethyl phosphite and stirred for 8 hours while heating at 180 ° C. After cooling to room temperature, excess phosphorous acid triethyl ester was distilled off under reduced pressure to obtain 24.1 g of a white oily compound (4-1) (yield 90%).

(B) Process:
In a 500 mL two-necked flask, 13 g (0.05 mol) of the compound (4-1) was added, purged with argon gas, 100 mL of dry tetrahydrofuran (THF) at 0 ° C., and 9.3 g (0.3%) of 28% sodium methoxide. 05 mol) was added and stirred as such for 30 minutes. Next, 7 g (0.05 mol) of the compound (5-1) was dissolved in 300 mL of dry THF and added to this reaction solution, followed by stirring at room temperature for 12 hours. Thereafter, the reaction solution was poured into ion exchange water, extracted with toluene, and the organic layer was washed 5 times with ion exchange water. Subsequently, after drying an organic layer with anhydrous sodium sulfate, it filtered and distilled off the solvent. Thereafter, the residue was purified by recrystallization with a mixed solvent of 20 mL of toluene / 100 mL of methanol to obtain 10.22 g of a white crystalline compound (6-1) (yield 85%).

(C) Process:
In a 2 L two-necked flask, 12 g (0.05 mol) of the compound (6-1), 0.0662 g (0.000189 mol) of (2-biphenyl) dicyclohexylphosphine, 0.0864 g of tris (dibenzylideneacetone) dipalladium (0) (0.0000944 mol), sodium t-butoxide 7.68 g (0.08 mol), and compound (7-1) 6.85 g (0.05 mol) were added, 500 mL of distilled o-xylene was added, and argon gas substitution was performed. And stirred for 5 hours while heating at 120 ° C. After cooling to room temperature, the reaction solution (organic layer) was washed three times with ion-exchanged water, and the organic layer was dried and adsorbed using anhydrous sodium sulfate and activated clay. Thereafter, filtration was performed, xylene was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: chloroform / hexane) to obtain 14.4 g of a solid compound (8-1) (yield 85%). ).

(D) Process:
A 500 mL flask is charged with 12.6 g (0.037 mol) of compound (8-1), 200 mL of toluene, 7.2 g (0.037 mol) of compound (9-1), and a catalytic amount of p-toluenesulfonic acid. The mixture was stirred for 2 hours while heating at 100 ° C. After cooling to room temperature, anhydrous sodium sulfate and activated clay were added to the reaction solution and dried, followed by filtration, and toluene was distilled off under reduced pressure. Thereafter, ethanol was added to the residue and heated to dissolve the residue, followed by cooling to precipitate crystals, yielding 16.3 g of crystalline compound (1-1) (yield 85%).

<Example 1>
5 parts by mass of an X-type metal-free phthalocyanine as a charge generating agent, 80 parts by mass of a compound (1-1) as a hole transporting agent, 50 parts by mass of a compound (10-1) as an electron transporting agent, and a binder resin 100 parts by mass of a certain polycarbonate resin was mixed and dispersed in 800 parts by mass of tetrahydrofuran as a solvent with a ball mill for 50 hours to prepare a coating solution for a single-layer type photoreceptor layer. Next, this coating solution is applied to a conductive substrate made of an aluminum base tube by a dip coating method and dried with hot air at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of 25 μm. A photoreceptor was obtained. The single layer type electrophotographic photosensitive member was subjected to an electrical property test and an appearance evaluation. The results are shown in Table 1.

<Example 2>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Example 3>
Example 1 except that Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent, and compound (10-2) was used instead of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Production of Compound (1-2)]
15.0 g of compound (1-2) was obtained in the same manner as compound (1-1) except that 6.15 g (0.05 mol) of compound (7-2) was used instead of compound (7-1). Obtained (yield 80%).

¹ H-NMR (300 MHz) was measured for the compound (1-2). As a solvent, CDCl ₃ was used, and TMS was used as a reference substance. It was confirmed that compound (1-2) was obtained. The ¹ H-NMR chart is shown in FIG.

<Example 4>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-2) was used instead of the compound (1-1) as the hole transport agent. The results are shown in Table 1.

<Example 5>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 4 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Example 6>
Example 4 except that Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent, and compound (10-2) was used instead of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Production of Compound (1-3)]
16.8 g of the compound (1-3) was obtained in the same manner as the compound (1-1) except that 9.25 g (0.05 mol) of the compound (7-3) was used instead of the compound (7-1). Obtained (yield 80%).

¹ H-NMR (300 MHz) of the compound (1-3) was measured. As a solvent, CDCl ₃ was used, and TMS was used as a reference substance. It was confirmed that compound (1-3) was obtained. A chart of ¹ H-NMR is shown in FIG.

<Example 7>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-3) was used instead of the compound (1-1) as the hole transporting agent. The results are shown in Table 1.

<Example 8>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 7 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Example 9>
Example 7 except that Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent, and compound (10-2) was used instead of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Production of Compound (1-4)]
Instead of compound (7-1), 6.15 g (0.05 mol) of compound (7-2) was used, and instead of compound (9-1), 4.9 g (0.037 mol) of compound (9-2) was used. ) 11.5 g of compound (1-4) was obtained in the same manner as compound (1-1) except that was used (yield 70%).

<Example 10>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-4) was used instead of the compound (1-1) as the hole transport agent. The results are shown in Table 1.

<Example 11>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Example 12>
Example 10 except that Y-type titanyl phthalocyanine was used in place of X-type metal-free phthalocyanine as the charge generating agent and compound (10-2) was used in place of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Production of Compound (1-5)]
Instead of compound (7-1), compound (1-5) 14.4 g was obtained in the same manner as compound (1-1), except that compound (7-4) 6.85 g (0.05 mol) was used. Obtained (yield 75%).

<Example 13>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-5) was used instead of the compound (1-1) as the hole transporting agent. The results are shown in Table 1.

<Example 14>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 13 except that the compound (10-2) was used instead of the compound (10-1) as the electron transport agent. The results are shown in Table 1.

<Example 15>
Example 13 except that Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent and compound (10-2) was used instead of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Production of Compound (1-6)]
Instead of compound (7-1), 6.15 g (0.05 mol) of compound (7-2) was used, and 2.7 g (0.037 mol) of compound (9-3) was used instead of compound (9-1). ) Was used in the same manner as compound (1-1) to obtain 11.3 g of compound (1-6) (yield 80%).

<Example 16>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (1-6) was used instead of the compound (1-1) as the hole transport agent. The results are shown in Table 1.

<Example 17>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 16 except that the compound (10-2) was used instead of the compound (10-1) as the electron transport agent. The results are shown in Table 1.

<Example 18>
Example 16 except that Y-type titanyl phthalocyanine was used in place of X-type metal-free phthalocyanine as the charge generating agent, and compound (10-2) was used in place of compound (10-1) as the electron transport agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Compound (2-1)]
<Comparative Example 1>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (2-1) was used instead of the compound (1-1) as the hole transporting agent. The results are shown in Table 1.

<Comparative example 2>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Comparative Example 1 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Comparative Example 3>
Comparative Example 1 except that Y-type titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent, and compound (10-2) was used instead of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Compound (2-2)]
<Comparative example 4>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (2-2) was used instead of the compound (1-1) as a hole transporting agent. The results are shown in Table 1.

<Comparative Example 5>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Comparative Example 4 except that the compound (10-2) was used instead of the compound (10-1) as the electron transport agent. The results are shown in Table 1.

<Comparative Example 6>
Comparative Example 4 except that Y-type titanyl phthalocyanine was used in place of X-type metal-free phthalocyanine as the charge generating agent and compound (10-2) was used in place of compound (10-1) as the electron transporting agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

[Compound (2-3)]
<Comparative Example 7>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound (2-3) was used instead of the compound (1-1) as the hole transport agent. The results are shown in Table 1.

<Comparative Example 8>
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Comparative Example 7 except that the compound (10-2) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 1.

<Comparative Example 9>
Comparative Example 7 except that Y-type titanyl phthalocyanine was used in place of X-type metal-free phthalocyanine as the charge generator, and compound (10-2) was used in place of compound (10-1) as the electron transport agent. Similarly, a single layer type electrophotographic photosensitive member was produced and evaluated. The results are shown in Table 1.

As is apparent from Table 1, the single layer type electrophotographic photosensitive member of the example had a lower residual potential than the single layer type electrophotographic photosensitive member of the comparative example. Further, when the appearance of the photoreceptor was evaluated, no crystallization was observed.
On the other hand, the single layer type electrophotographic photoreceptor of the comparative example had a high residual potential.

Since the enamine derivative of the present invention is excellent in solubility in a solvent and compatibility with a binder resin, an electrophotographic photoreceptor excellent in sensitivity can be obtained. The electrophotographic photosensitive member is expected to contribute to high speed and high performance of various image forming apparatuses.
Since the enamine derivative of the present invention has a high hole transport ability, it can be used for solar cells, electroluminescence devices and the like.

  DESCRIPTION OF SYMBOLS 10 Single layer type electrophotographic photosensitive member (electrophotographic photosensitive member) 12 Conductive substrate 14 Photosensitive member layer 20 Laminated electrophotographic photosensitive member (electrophotographic photosensitive member) 22 Charge transport layer (photosensitive member layer) 24 Charge generating layer (photosensitive member) Body layer)

Claims (2)

An enamine derivative, which is a compound represented by the following formula (1).

In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. 20 is an aryl group, and R ³ and R ⁴ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. A conductive substrate;
A photoreceptor layer provided on the conductive substrate,
An electrophotographic photoreceptor, wherein the photoreceptor layer is a layer containing the enamine derivative according to claim 1.

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