JP2007223987A - Diamine derivative and electrophotographic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a diamine derivative having excellent solubility in a solvent and compatibility with a binder resin; and to provide an electrophotographic photoreceptor having excellent sensitivity. <P>SOLUTION: The diamine derivative is represented by formula (1) (wherein, Ar<SP>1</SP>is an arylene group, an alkylene group or the like; Ar<SP>2</SP>and Ar<SP>3</SP>are each an aryl group or the like; R<SP>1</SP>to R<SP>12</SP>are each H or the like; R<SP>a</SP>and R<SP>b</SP>are each an alkyl group or an alkenyl group; and m and n are each an integer of 0-3). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a diamine 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, a compound represented by the following formula (2) is known (Patent Document 1).

However, the compound represented by the formula (2) has poor solubility in a solvent and compatibility with a binder resin, and the sensitivity of the obtained electrophotographic photosensitive member is insufficient.
JP 2005-289877 A

  Accordingly, an object of the present invention is to provide a diamine derivative that is excellent in solubility in a solvent and compatibility with a binder resin, and can obtain an electrophotographic photoreceptor excellent in sensitivity, and an electrophotographic photoreceptor excellent in sensitivity. It is to provide.

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

In formula (1), Ar ¹ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or an alkylene group which may have a substituent. Ar ² and Ar ³ are each an optionally substituted aryl group or an optionally substituted heterocyclic group, and R ^{1 to} R ¹² are each a hydrogen atom, a halogen atom, An atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent R ^a and R ^b are an optionally substituted alkyl group or an optionally substituted alkenyl group, and m and n are each an integer of 0 to 3.

  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 diamine derivative of the present invention. Features.

The diamine derivative of the present invention is excellent in solubility in a solvent and compatibility with a binder resin. Moreover, according to the diamine derivative of the present invention, an electrophotographic photoreceptor excellent in sensitivity can be obtained.
The electrophotographic photoreceptor of the present invention is excellent in sensitivity.

<Diamine derivative>
The diamine 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.

Ar ¹ is an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or an alkylene group which may have a substituent.
Examples of the arylene group include phenylene group, tolylene group, xylylene group, naphthylene group, anthrylene group, and phenanthrylene.
Examples of the divalent heterocyclic group include a pyridylene group, a pyrrolidinylene group, a thienylene group, and a furylidene group.
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a dimethylethylene group, a pentamethylene group, and a hexamethylene group.
Ar ¹ is preferably an arylene group or an alkylene group, more preferably a phenyl group or an ethylene group. The phenylene group may be a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group.

Ar ² and Ar ³ are each an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
Examples of the aryl group include phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, and the like.
Examples of the heterocyclic group include a pyridyl group, a pyrrolidinyl group, and a thienyl group.
As Ar ² and Ar ³ , an aryl group is preferable, and a phenyl group is more preferable.

R ^{1 to} R ¹² are each a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, Or it is the aralkyl group which may 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, hexyl group, and the like.
Examples of the aryl group include the above-described aryl groups.
Alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, t-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyl And an oxy group.
Examples of the aralkyl group include benzyl group, α-methylbenzyl group, phenethyl group, styryl group, cinnamyl group, 3-phenylpropyl group, 4-phenylbutyl group, 5-phenylpentyl group, and 6-phenylhexyl group. It is done.
As R < ¹ > -R < ¹² >, a hydrogen atom, an alkyl group, and an aryl group are preferable, and a hydrogen atom is more preferable.

R ^a and R ^b are an alkyl group which may have a substituent or an alkenyl group which may have a substituent.
Examples of the alkyl group include the above-described alkyl groups.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isobutenyl group, a 1-butenyl group, and a 2-butenyl group.
As R ^a and R ^b , an n-butyl group, a t-butyl group, and an isobutenyl group are preferable.
m and n are each an integer of 0 to 3, preferably 1 or 2, and more preferably 1, because the π bondability is increased and the sensitivity of the obtained electrophotographic photosensitive member is increased.

  Examples of compound (1) include compounds (1-1) to (1-4).

Compound (1) is produced as follows, for example, when Ar ² = Ar ³ , R ^{1 to} R ⁶ = R ^{7 to} R ¹² , R ^a = R ^b , and m = n. In the reaction formula, X ^{1 to} X ³ are each a halogen atom, and Ar ^{1 to} Ar ³ , R ^{1 to} R ¹² , R ^a , R ^b , m, and n are the same as those in the formula (1). is there.

(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. When there is too little triethyl phosphite, the yield of a compound (4) will worsen. If the amount of triethyl phosphite is too much, the amount of unreacted triethyl phosphite increases, which may make it difficult to purify the compound (4).
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:
In the presence of a catalyst, the compound (4) and the compound (5) are reacted in a solvent to obtain the compound (6) (Wittig reaction), and the 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 worsen. When there are too many compounds (4), there will be many unreacted compounds (4) and it will become difficult to refine | purify a compound (6).
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 used in the reaction 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 catalyst may be used individually by 1 type and may be used in combination of 2 or more type.

  The addition amount of the catalyst is preferably 1 to 1.5 mol with respect to 1 mol of the compound (4). When the addition amount of the catalyst is less than 1 mol, the reactivity between the compound (4) and the compound (5) may be significantly reduced. When the amount of the catalyst added 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; and aromatic hydrocarbons such as benzene and toluene.

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

The reaction ratio (molar ratio) between the compound (6) and the compound (7) is preferably 2: 1 to 2.5: 1. When there is too little compound (6), the yield of compound (8) will worsen. If the amount of the compound (6) is too large, the amount of unreacted compound (6) increases, and it may be difficult to purify the compound (8).
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 (O). 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 a catalyst or the like, compound (8) and compound (9) are reacted in a solvent to form compound (1) (coupling reaction), and compound (1) is extracted and purified.

The reaction ratio between the compound (8) and the compound (9) is preferably 1: 2 to 1: 2.5. When there is too little compound (8), the yield of compound (1) will worsen. When there are too many compounds (8), there will be many unreacted compounds (8) and it will become difficult to refine | purify a compound (1).
The reaction temperature is preferably 80 to 140 ° C., and the reaction time is preferably 2 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 catalyst and the solvent include the same as those in the step (c).

  Since the compound (1) described above has a larger number of nitrogen atoms per molecule than the compound (2), the sensitivity of the electrophotographic photoreceptor having the photoreceptor layer containing the compound (1) is improved. Further, since the compound (1) has three substituents having different nitrogen atoms, the compound (1) is excellent in solubility in a solvent and compatibility with a binder resin.

<Electrophotographic photoreceptor>
The electrophotographic photoreceptor of the present invention has a conductive substrate and a photoreceptor layer provided on the conductive substrate, and the photoreceptor layer contains the diamine 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 photosensitive member and (ii) a laminated type photosensitive member, and can be used for either a positive or negative charging type photosensitive member, has a simple structure, and is easy to manufacture. (I) A single-layer type photoreceptor is preferred because it can effectively suppress film defects when forming the photoreceptor layer, has few interfaces between layers, and easily improves optical characteristics.

(I) Single layer type photoreceptor:
FIG. 1 is a schematic cross-sectional view showing an example of a single layer type photoreceptor. The single layer type photoreceptor 10 has a conductive substrate 12 and a photoreceptor layer 14 provided on the conductive substrate 12.
The single-layer type photoreceptor 10 is not limited to that shown in FIG. 1, and the characteristics of the single-layer type photoreceptor 10 are provided between the conductive substrate 12 and the photoreceptor layer 14 as shown in FIG. The barrier layer 16 may be provided as long as it does not hinder, and a protective layer 18 may be provided on the surface of the photoreceptor layer 14 as shown in FIG.

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. Examples of other hole transporting agents include triarylamine compounds, oxadiazole compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole, 9- (4- Styryl compounds such as diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, indole compounds, Examples thereof include nitrogen-containing cyclic compounds such as oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, and 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.

  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.

  As electron transport agents, 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, etc. It is done. 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 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.
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.
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 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 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 photoreceptor:
FIG. 4 is a schematic cross-sectional view showing an example of a laminated photoreceptor. The multilayer 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. Have. In the laminated photoconductor 20, the charge generation layer 24 and the charge transport layer 22 constitute a photoconductor layer.

The multilayer photoreceptor 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 the charge generation layer 24 is provided on the charge transport layer 22. 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 photoreceptor.

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 photoreceptor is selected as a positive or negative charge type. For example, in a laminated photoreceptor 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 the charge transport agent for the charge transport layer. In this case, the photoreceptor is a negatively charged 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, binder and the like are the same as those of the single layer type photoreceptor.
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 photoreceptor.

Evaluation in Examples was performed as follows.
(Solubility)
The sample was added to tetrahydrofuran so that the concentration was 25% by mass, and the solubility was visually confirmed. The sample in which the solution became transparent was evaluated as ◯, and the sample remaining undissolved and the solution became cloudy was evaluated as ×.

(Electrical characteristics test)
A single layer type electrophotographic photosensitive member was installed in a drum sensitivity testing machine manufactured by GENTEC, and the single layer type electrophotographic photosensitive member was charged so that the initial surface potential V ₀ was + 700V. 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 measured as the residual potential V _L (V).
Further, an exposure amount (half exposure amount) at which the post-exposure potential of the single layer type electrophotographic photosensitive member becomes 1/2 of the initial surface potential was determined. The smaller the half exposure amount, the higher the sensitivity of the single layer type electrophotographic photosensitive member.

[Example 1]
(Production of Compound (1-1))
(A) Process:
A 200 mL flask was charged with 20 g (0.13 mol) of the compound (3-1) and 33 g (0.20 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 30 g of Compound (4-1) (yield 90%).

(B) Process:
Into a 500 mL two-necked flask, put 15 g (0.06 mol) of the compound (4-1), purged with argon gas, and added 100 mL of dried tetrahydrofuran (THF) and 11 g (0.06 mol) of 28% sodium methoxide. And stirred at 0 ° C. for 30 minutes. Next, 9 g (0.05 mol) of the compound (5-1) was dissolved in 300 mL of dry THF and added to this reaction solution, and the mixture was stirred 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. Next, the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off. Thereafter, the residue was purified by recrystallization with a mixed solvent of toluene 20 mL / methanol 100 mL to obtain 12 g of Compound (6-1) (yield 85%).

(C) Process:
In a 1 L flask, 10 g (0.04 mol) of compound (6-1), (2-biphenyl) dicyclohexylphosphine, 0.062 g (0.00018 mol), tris (dibenzylideneacetone) dipalladium (O) 0.08 (0 0.00009 mol) g, t-BuONa 5 g (0.05 mol), and compound (7-1) 2.2 g (0.02 mol) were added, 500 mL of o-xylene was added, argon gas replacement was performed, and the mixture was heated at 120 ° C. The mixture was stirred for 5 hours. After cooling to room temperature, the organic layer was washed three times with ion exchange water, the organic layer was dried and adsorbed using anhydrous sodium sulfate and activated clay, and xylene was distilled off under reduced pressure. Finally, the residue was purified by column chromatography (developing solvent: chloroform / hexane) to obtain 8.8 g of compound (8-1) (yield 85%).

(D) Process:
In a 300 mL two-necked flask, 0.9 g (0.00677 mol) of compound (9-1), 0.012 g (0.0000339 mol) of (2-biphenyl) dicyclohexylphosphine, tris (dibenzylideneacetone) dipalladium (O) 0 .016 g (0.0000169 mol), t-BuONa 1.0 g (0.01016 mol), and compound (8-1) 7.0 g (0.0135 mol) were added, o-xylene 500 mL was added, and argon gas substitution was performed. The mixture was stirred for 3 hours while heating at 120 ° C. After cooling to room temperature, the organic layer was washed three times with ion exchange water, the organic layer was dried and adsorbed using anhydrous sodium sulfate and activated clay, and xylene was distilled off under reduced pressure. Finally, the residue was purified by column chromatography (developing solvent: chloroform / hexane) to obtain 6.4 g of compound (1-1) (yield 75%).

  The solubility of the compound (1-1) was evaluated. The results are shown in Table 1.

(Manufacture of electrophotographic photoreceptors)
5 parts by mass of an X-type metal-free phthalocyanine that is a charge generating agent, 60 parts by mass of a compound (1-1) that is a hole transport agent, and 100 parts by mass of a polycarbonate resin that is a binder resin, 800 parts by mass of tetrahydrofuran that is a solvent Then, a coating solution for a single-layer type photosensitive layer was prepared by mixing and dispersing in a ball mill for 50 hours. Next, the coating solution is applied on a conductive substrate made of an aluminum base tube by dip coating, and dried with hot air at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of 25 μm. Got the body. The single layer type electrophotographic photosensitive member was subjected to an electrical property test. The results are shown in Table 2.

[Example 2]
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that 50 parts by mass of the compound (10-1) as an electron transfer agent was added to the coating solution. The results are shown in Table 2.

Example 3
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2 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 2.

Example 4
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 2 except that the compound (10-3) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 2.

Example 5
(Production of Compound (1-2))
Compound (7-2) was used instead of compound (7-1), and compound (9-2) was used instead of compound (9-1). 1-2) was produced.

  The solubility of the compound (1-2) was evaluated. The results are shown in Table 1.

(Manufacture of electrophotographic photoreceptors)
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 2.

Example 6
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 5 except that 50 parts by mass of the compound (10-1) as an electron transfer agent was added to the coating solution. The results are shown in Table 2.

Example 7
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 6 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 2.

Example 8
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 6 except that the compound (10-3) was used instead of the compound (10-1) as the electron transport agent. The results are shown in Table 2.

Example 9
(Production of Compound (1-3))
Compound (1-3) was produced in the same manner as in Example 1, except that 0.9 g (0.00657 mol) of compound (9-3) was used instead of 0.9 g of compound (9-1).

  The solubility of the compound (1-3) was evaluated. The results are shown in Table 1.

(Manufacture of electrophotographic photoreceptors)
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 2.

Example 10
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that 50 parts by mass of the compound (10-1) as an electron transfer agent was added to the coating solution. The results are shown in Table 2.

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 2.

Example 12
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 10 except that the compound (10-3) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 2.

Example 13
(Production of Compound (1-4))
Compound (1-4) was produced in the same manner as in Example 1, except that 1.2 g (0.0203 mol) of compound (7-4) was used instead of 2.2 g of compound (7-1).

  The solubility of the compound (1-4) was evaluated. The results are shown in Table 1.

(Manufacture of electrophotographic photoreceptors)
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 2.

Example 14
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 13 except that 50 parts by mass of the compound (10-1) as an electron transfer agent was added to the coating solution. The results are shown in Table 2.

Example 15
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 14 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 2.

Example 16
A single-layer electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 14 except that the compound (10-3) was used instead of the compound (10-1) as the electron transfer agent. The results are shown in Table 2.

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

Since the diamine 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 diamine derivative of the present invention has a high hole transport ability, it can be used for solar cells, electroluminescence devices, and the like.

It is a schematic sectional view showing an example of a single layer type photoreceptor. It is a schematic sectional drawing which shows the other example of a single layer type photoreceptor. It is a schematic sectional drawing which shows the other example of a single layer type photoreceptor. It is a schematic sectional drawing which shows an example of a laminated type photoreceptor. It is a schematic sectional drawing which shows the other example of a laminated type photoreceptor.

Explanation of symbols

10 Single layer type photoreceptor (electrophotographic photoreceptor)
12 Conductive Substrate 14 Photoreceptor Layer 20 Multilayer Photoreceptor (Electrophotographic Photoreceptor)
22 Charge transport layer (photoreceptor layer)
24 Charge generation layer (photoreceptor layer)

Claims (2)

The diamine derivative which is a compound represented by following formula (1).

In formula (1), Ar ¹ represents an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or an alkylene group which may have a substituent. Ar ² and Ar ³ are each an optionally substituted aryl group or an optionally substituted heterocyclic group, and R ^{1 to} R ¹² are each a hydrogen atom, a halogen atom, An atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent R ^a and R ^b are an optionally substituted alkyl group or an optionally substituted alkenyl group, and m and n are each an integer of 0 to 3. A conductive substrate;
A photoreceptor layer provided on the conductive substrate,
An electrophotographic photoreceptor, wherein the photoreceptor layer is a layer containing the diamine derivative according to claim 1.

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