JP2016051027A - Positively-charged single-layer electrophotographic photoreceptor, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positively-charged single-layer electrophotographic photoreceptor that can suppress the occurrence of transfer memory while suppressing crystallization of the surface of a photoreceptor, and an image forming apparatus that can suppress the occurrence of image defects.SOLUTION: A positively-charged single-layer electrophotographic photoreceptor 1 includes a conductive base material 2 and a single-layer photosensitive layer 3 that is arranged on the conductive base material. The single-layer photosensitive layer includes at least a charge generating agent, hole transport agent, electron transport agent, and binder resin. The hole transport agent includes a triphenylamine derivative represented by the following general formula (1).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a positively charged single layer type electrophotographic photosensitive member and an image forming apparatus.

  As an electrophotographic photoreceptor provided in an electrophotographic image forming apparatus, an inorganic photoreceptor and an organic photoreceptor are used. The inorganic photoreceptor includes a photosensitive layer made of an inorganic material such as selenium and amorphous silicon. The organic photoreceptor mainly includes a photosensitive layer made of an organic material such as a binder resin, a charge generator, and a charge transport material. Among these photoreceptors, organic photoreceptors are easy to manufacture compared to inorganic photoreceptors, and the photosensitive layer materials can be selected from a wide range of materials, and the degree of freedom in design is high. Widely used.

  As the organic photoreceptor, a single-layer organic photoreceptor and a laminated organic photoreceptor are used. The single layer type organic photoreceptor includes a charge generating agent and a charge transporting agent in the same layer. In the multilayer organic photoreceptor, a charge generation layer containing a charge generation agent and a charge transport layer containing a charge transfer agent are laminated on a conductive substrate. It is known that a single-layer type organic photoreceptor is simple in structure and easy to manufacture and can suppress the occurrence of film defects, as compared with a multilayer organic photoreceptor.

An image forming process including the following steps 1) to 5) is performed using such an electrophotographic photosensitive member.
1) a step of charging the surface of the electrophotographic photosensitive member,
2) exposing the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image on the surface of the photosensitive member;
3) a step of developing the electrostatic latent image as a toner image in a state where a developing bias voltage is applied;
4) A step of transferring the formed toner image from the electrophotographic photosensitive member to the transfer target, and 5) A step of heating and fixing the toner image transferred to the transfer target.

  However, in such an image forming process, since the electrophotographic photosensitive member is rotated and used, a transfer memory may be generated due to the transfer process. Specifically, it is as follows. In the charging step, the surface of the image carrier is uniformly charged to a constant potential (for example, positive polarity). Subsequently, through an exposure process and a development process, in the transfer process, a transfer bias (for example, negative polarity) opposite to the charge is applied to the electrophotographic photosensitive member through the transfer target. Due to the influence of the applied transfer bias, the potential of the non-exposed area on the surface of the image carrier may be greatly lowered. On the other hand, the potential of the exposed area on the surface of the photoconductor hardly decreases because toner adheres on the photoconductor. Due to the effect of lowering the potential of the non-exposed area, even if the surface of the image carrier is to be uniformly charged in the next charging step, the non-exposed area is brought to a desired potential (for example, desired positive polarity). It becomes difficult to charge the exposed area and the non-exposure amount area may have different charging potentials. Such a phenomenon that the charging ability of the non-exposure amount region is lowered is called a transfer memory. The region where the desired potential cannot be obtained in the next charging step (specifically, the non-exposed region of the previous rotation on the surface of the image carrier) has a potential (for example, a positive potential) than the other regions. Therefore, it is easy to attract toner (for example, positive toner). As a result, an image defect such as an image ghost occurs.

  Further, positively charged single layer type electrophotographic photosensitive members and negatively charged single layer type electrophotographic photosensitive members are used as the single layer type electrophotographic photosensitive member. In addition, a contact charging method and a non-contact charging method are used as charging methods for the electrophotographic photosensitive member. Among these, the following photosensitivity is obtained from the point of life of the electrophotographic photosensitive member and the fact that an oxidizing gas such as ozone that adversely affects the office environment is hardly generated when the surface of the electrophotographic photosensitive member is charged. It is preferable to use a body and / or a charged part. That is, it is preferable to use a positively charged single layer type electrophotographic photosensitive member, and it is more preferable to use a contact charging type charging unit and a positively charged single layer type electrophotographic photosensitive member in combination. However, when a contact charging type charging unit and a positively charged single layer type electrophotographic photosensitive member are used in combination, there is a problem that a transfer memory is particularly likely to occur.

  In view of the above circumstances, there is a demand for a positively charged single layer type electrophotographic photosensitive member that can suppress the generation of a transfer memory during image formation. In order to suppress the generation of the transfer memory, it is effective to use a charge transport agent having a good charge transport capability. As a charge transport agent having a good charge transport ability, various triarylamine derivatives have been proposed as a hole transport agent.

  An arylamine compound is known as a charge transporting agent that can be used in an electrophotographic organic photoreceptor (Patent Document 1). Similarly, an arylamine composition containing a geometric isomer (cis type and trans type) arylamine compound in a specific ratio is known (Patent Document 2).

Japanese Patent Laid-Open No. 9-244278 JP 2002-080432 A

  However, even when the arylamine compound described in Patent Document 1 or the arylamine composition described in Patent Document 2 is used as a charge transport agent, it is difficult to suppress the generation of a transfer memory.

  In view of the above problems, the present invention provides a positively charged single layer type electrophotographic photosensitive member capable of suppressing the generation of a transfer memory while suppressing the crystallization of the surface of the photosensitive member. The present invention also provides an image forming apparatus that can suppress the occurrence of image defects by including such a positively charged single layer type electrophotographic photosensitive member.

  The positively charged single layer type electrophotographic photosensitive member of the present invention comprises a conductive substrate and a single layer type photosensitive layer disposed on the conductive substrate. The single-layer type photosensitive layer includes at least a charge generator, a hole transport agent, an electron transport agent, and a binder resin. The said hole transport agent contains the triphenylamine derivative (henceforth "triphenylamine derivative (1)") represented by following General formula (1).

In the general formula (1), R _{1 to} R ₇ are independently the same or different from each other, and each represents a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a substituent. It is selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms which may have and an aryl group having 6 to 12 carbon atoms which may have a substituent. k, l, m, n, o, and p each represent an integer of 0 or more and 4 or less. When k, l, m, n, o, or p represents an integer of 2 or more, a plurality of corresponding R ₃ , R ₄ , R ₅ , R ₅ , R ₆ , or R present in the same aromatic ring Each of ₇ may be the same or different.

  The image forming apparatus of the present invention includes an image carrier, a charging unit, an exposure unit, a developing unit, and a transfer unit. The charging unit charges the surface of the image carrier. The exposure unit exposes the charged surface of the image carrier to form an electrostatic latent image on the surface of the image carrier. The developing unit develops the electrostatic latent image as a toner image. The transfer unit transfers the toner image from the image carrier to a transfer target. The image carrier is the positively charged single layer type electrophotographic photosensitive member described above.

  According to the present invention, it is possible to obtain a positively charged single layer type electrophotographic photosensitive member capable of suppressing generation of a transfer memory while suppressing crystallization of the surface of the photosensitive member. Further, by providing such a positively charged single layer type electrophotographic photosensitive member, an image forming apparatus capable of suppressing the occurrence of image defects can be obtained.

(A), (b), and (c) are schematic sectional views showing the structure of a positively charged single layer type electrophotographic photosensitive member according to an embodiment of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus including a positively charged single layer type electrophotographic photosensitive member according to an embodiment of the present invention. FIG. 3 is a schematic diagram illustrating a configuration of another aspect of an image forming apparatus including a positively charged single layer type electrophotographic photoreceptor according to an embodiment of the present invention. 2 is a ¹ H-NMR spectrum of a compound represented by the formula (HT-1). 2 is a ¹ H-NMR spectrum of a compound represented by the formula (HT-2). 2 is a ¹ H-NMR spectrum of a compound represented by the formula (HT-3). It is a ¹ H-NMR spectrum of a compound denoted by a formula (HT-4). 2 is a ¹ H-NMR spectrum of a compound represented by the formula (HT-5).

  Hereinafter, although embodiment of this invention is described in detail, this invention is not limited to the following embodiment at all. The present invention can be implemented with appropriate modifications within the scope of the object of the present invention. In addition, about the location where description overlaps, although description may be abbreviate | omitted suitably, the summary of invention is not limited.

[First Embodiment: Positively Charged Single-Layer Electrophotographic Photoreceptor]
The first embodiment relates to a positively charged single layer type electrophotographic photosensitive member (hereinafter sometimes simply referred to as “photosensitive member”). Hereinafter, the positively charged single layer type electrophotographic photosensitive member according to the present embodiment will be described with reference to FIG.

  The positively charged single layer type electrophotographic photosensitive member 1 includes a conductive substrate 2 and a single layer photosensitive layer 3 disposed on the conductive substrate 2. The single-layer type photosensitive layer 3 includes at least a charge generator, a hole transport agent, an electron transport agent, and a binder resin. The hole transport agent contains a triphenylamine derivative (1). Compound (1) will be described later.

  As described above, the single-layer photosensitive layer 3 of the photoreceptor according to the first embodiment includes the triphenylamine derivative (1) as a hole transport agent. As a result, it is possible to obtain the positively charged single layer type electrophotographic photosensitive member 1 that not only suppresses the crystallization of the surface of the photosensitive member but also can suppress the transfer memory. This is considered due to the following reasons.

The triphenylamine derivative (1) has a specific substituent (R ₁ and R ₂ ) at the ortho position of the phenyl group bonded to the nitrogen atom present at both ends of the biphenyl moiety. By having such a structure, the triphenylamine derivative (1) tends to be excellent in solubility in a solvent and / or compatibility in a binder resin. Therefore, the triphenylamine derivative (1), which is a hole transport agent, can be uniformly dispersed in the single-layer type photosensitive layer 3.

  The single-layer type photosensitive layer 3 in which the triphenylamine derivative (1), which is a hole transport agent, is uniformly dispersed tends to be excellent in charge mobility. In the photoreceptor 1 having such a single-layer type photosensitive layer 3, it is possible to quickly move a charge having a polarity opposite to that applied when a transfer bias is applied. Although it is the electron transport agent that transports the charge of the opposite polarity, the electron transport agent and the triphenylamine derivative (1) of the hole transport agent are mixed together in the single-layer photosensitive layer 3 to thereby transport the electron. This is because the compatibility of the agent with the binder resin is increased and the function of the electron transport agent is enhanced. For this reason, the difference between the potential in the white paper portion before application of the transfer bias and the potential in the white paper portion when the transfer bias is applied tends to decrease. As a result, the potential on the photoreceptor 1 is stabilized, and the generation of transfer memory can be suppressed. In addition, it is considered that the suppression of the generation of the transfer memory is particularly effective in an image forming apparatus including a contact-type charging unit in which charging is performed under conditions more severe for the photosensitive member 1 than a non-contact type charging unit. .

  Further, as described above, the triphenylamine derivative (1) having a specific structure tends to be excellent in solubility in a solvent and / or compatibility in a binder resin. Therefore, it is possible to suppress the triphenylamine derivative (1) from being crystallized in the single layer type photosensitive layer 3 when the single layer type photosensitive layer 3 is formed. As a result, crystallization on the surface of the photoreceptor can be suppressed.

  For the above reasons, according to the positively charged single layer type electrophotographic photosensitive member 1 of the present embodiment, it is possible to effectively suppress the generation of a transfer memory while suppressing the crystallization of the surface of the photosensitive member.

  Next, the positively charged single layer type electrophotographic photoreceptor 1 according to the present embodiment will be described. The photoreceptor 1 includes a conductive substrate 2 and a single-layer type photosensitive layer 3. The single-layer type photosensitive layer 3 is disposed on the conductive substrate 2.

  The photoreceptor 1 is not particularly limited as long as it includes the conductive substrate 2 and the single-layer type photosensitive layer 3. For example, as shown in FIG. 1A, a single-layer type photosensitive layer 3 may be directly provided on a conductive substrate 2. Alternatively, as shown in FIG. 1B, a suitable intermediate layer 4 may be provided between the conductive substrate 2 and the single-layer type photosensitive layer 3. Further, as shown in FIGS. 1A and 1B, the single-layer type photosensitive layer 3 may be exposed as the outermost layer. Alternatively, as shown in FIG. 1C, a protective layer 5 may be appropriately provided on the single-layer type photosensitive layer 3.

  Hereinafter, the conductive substrate 2 and the single-layer type photosensitive layer 3 will be described.

(1) Conductive substrate The conductive substrate 2 is not particularly limited as long as it can be used as the conductive substrate of the positively charged single layer type electrophotographic photosensitive member 1. As the conductive substrate 2, a conductive substrate formed of a material having at least a surface portion having conductivity can be used. Examples of the conductive substrate 2 include a conductive substrate composed of a conductive material; and a conductive substrate on which a plastic material is coated with a conductive material. Examples of the conductive material include aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass. These conductive materials may be used alone or in combination of two or more (for example, as an alloy). Among these materials having conductivity, aluminum or an aluminum alloy is preferable because charge transfer from the single-layer type photosensitive layer 3 to the conductive substrate 2 is good.

  The shape of the conductive substrate 2 can be appropriately selected according to the structure of the image forming apparatus to be used. For example, a sheet-like conductive substrate or a drum-shaped conductive substrate can be used. Further, the thickness of the conductive substrate 2 can be appropriately selected according to the shape of the conductive substrate 2.

(2) Single-layer type photosensitive layer The single-layer type photosensitive layer 3 provided in the positively charged single-layer type electrophotographic photoreceptor 1 includes at least a charge generating agent, a hole transport agent, an electron transport agent, and a binder resin. Hereinafter, the charge generator, the hole transport agent, the electron transport agent, and the binder resin contained in the single-layer type photosensitive layer 3 will be described. Further, additives that may be included in the single-layer type photosensitive layer 3 as necessary will be described.

(2-1) Charge generator The charge generator is not particularly limited as long as it is a charge generator for a positively charged single layer type electrophotographic photosensitive member. Examples of the charge generator include X-type metal-free phthalocyanine (x-H ₂ Pc), titanyl phthalocyanine (TiOPc), perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine pigment, SQUALINE 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, tris Examples thereof include phenylmethane pigments, selenium pigments, toluidine pigments, pyrazoline pigments, and 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 or Y-type titanyl phthalocyanine 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 or more and 550 nm or less), an ansanthrone pigment or a perylene pigment is suitable as a charge generator. Used for.

  In the photoreceptor 1, the content of the charge generating agent is preferably 0.1 parts by mass or more and 50 parts by mass or less, and 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferable.

(2-2) Hole transport agent The hole transport agent contains a triphenylamine derivative represented by the following general formula (1).

In general formula (1), R _{1 to} R ₇ are independently the same or different from each other, and each have a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent. It is selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms which may be substituted, and an aryl group having 6 to 12 carbon atoms which may have a substituent. k, l, m, n, o, and p each represent an integer of 0 or more and 4 or less. When k, l, m, n, o, or p represents an integer of 2 or more, a plurality of corresponding R ₃ , R ₄ , R ₅ , R ₅ , R ₆ , or R present in the same aromatic ring Each of ₇ may be the same or different.

R ₁ and R _{2 in} the general formula (1) are each preferably an alkyl group having 1 to 6 carbon atoms. This is because the degree of spread of π electrons can be adjusted to a suitable state, and charge transport efficiency can be improved.

For the same reason, R _{1 to} R ₄ in the general formula (1) are independently the same or different and each is an alkyl group having 1 to 6 carbon atoms, and k and l are each an integer of 1. It is more preferable to represent.

For the same reason, R ₅ in the general formula (1) is preferably an alkyl group having 1 to 6 carbon atoms.

  Further, the triphenylamine derivative (1) of the present embodiment is a trans type. Therefore, it may be presumed that it has a structure that is easily crystallized when contained in the single-layer type photosensitive layer 3 as compared with the cis type. However, by having a specific substituent, it is possible to obtain a single-layer type photosensitive layer 3 in which crystallization is suppressed.

In R < ₁ > -R < ₇ > of General formula (1), a halogen atom is a fluorine, chlorine, or bromine, for example.

In R _{1 to} R ₇ of the general formula (1), an alkyl group having 1 to 6 carbon atoms is, for example, 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 a methyl group, an ethyl group, or a t-butyl group.

In R _{1 to} R ₇ of the general formula (1), an alkoxy group having 1 to 6 carbon atoms is, for example, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an s-butoxy group, A t-butoxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, or a hexyloxy group. The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group.

In R _{1 to} R ₇ of the general formula (1), the aryl group having 6 to 12 carbon atoms is, for example, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, an anthryl group, or a phenanthryl group. is there. The aryl group having 6 to 12 carbon atoms is preferably a phenyl 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, an alkyl group, an alkoxy group, or an aryl group is mentioned, Preferably it is a C1-C6 alkyl group, a C1-C6 alkoxy group, or carbon An aryl group having 6 to 12 atoms is exemplified. Examples of the alkyl group having 1 to 6 carbon atoms as the substituent are the same groups as those exemplified as the alkyl group having 1 to 6 carbon atoms in R _{1 to} R ₇ in the general formula (1). 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 to} R ₇ in the general formula (1). 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 to} R ₇ in the general formula (1). Is mentioned.

In the general formula (1), k and l preferably represent an integer of 1. This is because crystallization of the triphenylamine derivative (1) in the monolayer type photosensitive layer 3 can be further suppressed by reducing the number of substituents on the benzene ring to which R ₃ or R ₄ is bonded. .

  Specific examples of the triphenylamine derivative (1) are represented by the following formulas (HT-1) to (HT-8). Hereinafter, the formula (HT-1) to the triphenylamine derivative (HT-8) may be described as the triphenylamine derivative (HT-1) to (HT-8), respectively.

Among the specific examples described above, ¹ H-NMR spectra of triphenylamine derivatives (HT-1) to (HT-5) are shown in FIGS. 4 to 8, respectively.

  Hereinafter, the manufacturing method of a triphenylamine derivative (1) is demonstrated. The production method of the triphenylamine derivative (1) includes reactions represented by the following reaction formulas (R-1), (R-2), and (R-3). Such a production method is intended to produce a trans-type triphenylamine derivative, and it is not necessary to consider producing a triphenylamine derivative having geometrical isomers of cis-type and trans-type. Therefore, it is not necessary to specify the reaction conditions at the time of synthesis or the compounding ratio of the materials, and the triphenylamine derivative can be produced with an easy operation and in a high yield.

In the reaction formulas (R-1), (R-2), and (R-3), R _{1 to} R ₇ , k, l, m, n, o, and p are R ₁ in the general formula (1). ~ R ₇ , k, l, m, n, o, and p are synonymous. X represents a halogen atom such as chlorine or fluorine.

  In the reaction represented by the reaction formula (R-1), a compound (aniline derivative) represented by the general formulas (2) and (3) and a compound (biphenyl derivative) represented by the general formula (4) Reaction is performed to obtain a compound represented by the general formula (5) (biphenylamine derivative).

  The reaction ratio [(aniline derivative) :( biphenyl derivative)] between the aniline derivative and the biphenyl derivative is preferably 1: 1 or more and 2: 1 or less by molar ratio. If the number of moles of the biphenyl derivative relative to the number of moles of the aniline derivative is too small, the yield of the biphenylamine derivative represented by the general formula (5) may be excessively lowered. On the other hand, if the number of moles of the biphenyl derivative relative to the number of moles of the aniline derivative is excessive, the excess biphenyl derivative may remain excessively unreacted and the purification of the biphenylamine derivative may be difficult.

  Regarding the reaction represented by the reaction formula (R-1), the reaction temperature is preferably 80 ° C. or higher and 140 ° C. or lower. The reaction time is preferably 2 hours or more and 10 hours or less.

  In the reaction represented by the reaction formula (R-1), it is preferable to use a palladium compound as a catalyst. By using a palladium compound as a catalyst, the activation energy in the reaction represented by the reaction formula (R-1) is effectively reduced. As a result, the yield of the biphenylamine derivative can be improved.

  Specific 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). A palladium compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the palladium compound is preferably 0.0005 mol or more and 20 mol or less, and 0.001 mol or more and 1 mol or less with respect to 1 mol of the biphenyl derivative represented by the general formula (4). More preferred.

  Such a palladium compound may have a structure including a ligand. Thereby, the reactivity of reaction represented by Reaction formula (R-1) 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 preferably 0.0005 mol or more and 20 mol or less, and 0.001 mol or more and 1 mol or less with respect to 1 mol of the biphenyl derivative represented by the general formula (4). Is more preferable.

  In addition, the reaction represented by the reaction formula (R-1) is preferably performed in the presence of a base.

  By performing the reaction represented by the reaction formula (R-1) in the presence of a base, the hydrogen halide generated in the reaction system is quickly neutralized and the catalytic activity is improved. As a result, the yield of the biphenylamine derivative represented by the general formula (5) can be improved.

  The base may be an inorganic base or an organic base. Examples of the organic base include, but are not limited to, alkali metal alkoxides (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, or potassium tert-butoxide. ) Is preferred, and sodium-tert-butoxide is more preferred. In addition, examples of the inorganic base include tripotassium phosphate and cesium fluoride.

  When 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1 mol of the biphenyl derivative represented by the general formula (4), the addition amount of the base is preferably 1 mol or more and 10 mol or less. More preferably, it is at least 5 mol and not more than 5 mol.

  The reaction represented by the reaction formula (R-1) can be carried out in a solvent. Examples of the solvent include xylene (o-, m-, or p-), toluene, tetrahydrofuran, or dimethylformamide.

  Next, the reaction represented by the reaction formula (R-2) will be described. In the reaction formula (R-2), the benzene derivative represented by the general formula (6) and the triethyl phosphite represented by the general formula (7) are reacted to represent the general formula (8). To obtain a phosphonate derivative.

  The reaction ratio [(benzene derivative) :( triethyl phosphite)] between the benzene derivative and triethyl phosphite is preferably 1: 1 or more and 1: 2.5 or less in molar ratio. If the number of moles of triethyl phosphite relative to the number of moles of the benzene derivative is too small, the yield of the phosphonate derivative may be excessively lowered. On the other hand, if the number of moles of triethyl phosphite relative to the number of moles of benzene derivative is excessive, unreacted triethyl phosphite may remain excessively after the reaction, making it difficult to purify the phosphonate derivative.

  Regarding the reaction between the benzene derivative and triethyl phosphite, the reaction temperature is preferably from 160 ° C. to 200 ° C., and the reaction time is preferably from 2 hours to 16 hours.

  Next, the phosphonate derivative represented by the general formula (8) and the cinnamaldehyde derivative represented by the general formulas (9) and (10) prepared separately are reacted, and the general formulas (11) and (12) The diphenylbutadiene derivative represented is obtained (Wittig reaction).

  The reaction ratio [(phosphonate derivative) :( cinnamaldehyde derivative)] between the phosphonate derivative and the cinnamaldehyde derivative is preferably 1: 1 or more and 1: 2.5 or less in molar ratio. If the number of moles of the cinnamaldehyde derivative relative to the number of moles of the phosphonate derivative is too small, the yield of the diphenylbutadiene derivative may be excessively lowered. If the number of moles of the cinnamaldehyde derivative relative to the number of moles of the phosphonate derivative is excessive, unreacted cinnamaldehyde derivatives may remain excessively, making it difficult to purify the diphenylbutadiene derivative.

  The Wittig reaction can be carried out in the presence of a catalyst. Examples of the catalyst used include sodium alkoxide (sodium methoxide or sodium ethoxide), metal hydride (sodium hydride or potassium hydride), or metal salt (eg, n-butyllithium). These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type. The addition amount of such a catalyst is preferably 1 mol or more and 2 mol or less with respect to 1 mol in total of the cinnamaldehyde derivatives. If the amount of such a catalyst added is too small, the reactivity may be significantly reduced. On the other hand, if the amount of the catalyst added is excessive, it may be difficult to control the reaction.

  Regarding the reaction between the phosphonate derivative and cinnamaldehyde, the reaction temperature is preferably 0 ° C. or higher and 70 ° C. or lower, and the reaction time is preferably 10 hours or longer and 20 hours or shorter.

  The reaction represented by the reaction formula (R-2) is performed, for example, in a solvent. Examples of the solvent include ethers (diethyl ether, tetrahydrofuran, or dioxane), halogenated hydrocarbons (methylene chloride, chloroform, or dichloroethane), or aromatic hydrocarbons (benzene or toluene).

  Next, the reaction represented by the reaction formula (R-3) will be described. In this reaction, the biphenylamine derivative represented by the formula (5) obtained by the reaction formula (R-1) and the formulas (11) and (12) obtained by the reaction formula (R-2) The triphenylamine derivative (1) which is the final target product is synthesized by reacting with the diphenylbutadiene derivative represented.

  The reaction ratio of biphenylamine derivative to diphenylbutadiene derivative [(number of moles of biphenylamine derivative) :( total number of moles of diphenylbutadiene derivatives represented by formulas (11) and (12))] is 1: 1 or more and 1 Is preferably 5 or less, more preferably 1: 1 or more and 1: 3 or less. If the number of moles of the diphenylbutadiene derivative is too small relative to the number of moles of the biphenylamine derivative, the yield of the triphenylamine derivative (1) may be excessively lowered. On the other hand, if the number of moles of the diphenylbutadiene derivative is excessive with respect to the number of moles of the biphenylamine derivative, after the reaction, the excess diphenylbutadiene derivative remains excessively unreacted, and the triphenylamine derivative (1) Purification may be difficult.

  Regarding the reaction represented by the reaction formula (R-3), the reaction temperature is preferably 80 ° C. or more and 140 ° C. or less, and the reaction time is preferably 2 hours or more and 10 hours or less.

  Moreover, it is preferable to use a palladium compound as a catalyst for the reaction represented by the reaction formula (R-3).

  By using a palladium compound as a catalyst, the activation energy in the reaction represented by the reaction formula (R-3) is effectively reduced. As a result, the yield of the triphenylamine derivative (1) 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). 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, more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the biphenylamine derivative.

  In addition, the reaction represented by the reaction formula (R-3) is preferably performed in the presence of a base.

  By performing the reaction represented by the reaction formula (R-3) in the presence of a base, the hydrogen halide generated in the reaction system is quickly neutralized and the catalytic activity is improved. As a result, the yield of the triphenylamine derivative (1) can be improved.

  The base may be an inorganic base or an organic base. Examples of the organic base include, but are not limited to, alkali metal alkoxides (sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, or potassium tert-butoxide. ) Is preferred, and sodium-tert-butoxide is more preferred. In addition, examples of the inorganic base include tripotassium phosphate and cesium fluoride.

  When 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1 mol of the biphenylamine derivative, the addition amount of the base is preferably 1 mol or more and 10 mol or less, and preferably 1 mol or more and 5 mol or less. It is more preferable.

  Such a palladium compound may have a structure including a ligand. Thereby, the reactivity of reaction represented by Reaction formula (R-3) 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 preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the biphenylamine derivative.

  The reaction represented by the reaction formula (R-3) can be carried out in a solvent. Examples of the solvent include xylene (specifically, o-, m-, or p-xylene), toluene, tetrahydrofuran, or dimethylformamide.

  In the manufacturing method of this embodiment, in addition to the step of performing the reaction represented by the reaction formula (R-1), (R-2) or (R-3), an appropriate step may be included as necessary. Good.

  In the positively charged single layer type electrophotographic photosensitive member 1, the content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferable that the amount is not more than parts.

(2-3) Electron transport agent The monolayer type photosensitive layer 3 contains an electron transport agent. As a result, the single-layer type photosensitive layer 3 can transport electrons, and it is easy to impart bipolar (bipolar) characteristics to the single-layer type photosensitive layer 3.

  Examples of the electron transfer agent include quinone compounds (specifically, naphthoquinone compounds, diphenoquinone compounds, anthraquinone compounds, azoquinone compounds, nitroanthraquinone compounds, or dinitroanthraquinone compounds), malononitrile compounds, thiopyrans. Compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, di Nitrobenzene, dinitroanthracene, dinitroacridine, succinic anhydride, maleic anhydride, or dibromomaleic anhydride

  More specifically, examples of the electron transfer agent include electron transfer agents represented by the following formulas (ETM-I) to (ETM-IV).

In formulas (ETM-I) to (ETM-IV), R _{11 to} R ₂₂ are independently the same or different from each other, and each has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. May have an alkenyl group, an alkoxy group that may have a substituent, an aralkyl group that may have a substituent, an aromatic hydrocarbon group that may have a substituent, and a substituent. Selected from the group consisting of heterocyclic groups. R ₂₃ may have a halogen atom, a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. It is selected from the group consisting of a good aralkyl group, an aromatic hydrocarbon group which may have a substituent, and a heterocyclic group which may have a substituent.

In R _{11 to} R ₂₃ in formulas (ETM-I) to (ETM-IV), the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferably, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group, a tert-butyl group, or a 1,1-dimethylpropyl group is more preferable. Such an alkyl group may be any of a linear alkyl group, a branched alkyl group, a cyclic alkyl group, or an alkyl group obtained by combining these. Examples of the substituent that such an alkyl group may have include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. The number of substituents that such an alkyl group may have is not particularly limited, but is preferably 3 or less.

In R _{11 to} R ₂₃ in the formulas (ETM-I) to (ETM-IV), examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms, and preferably 2 to 6 carbon atoms. And more preferably an alkenyl group having 2 to 4 carbon atoms. The alkenyl group may be any of a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, or a combination of these alkenyl groups. Examples of the substituent that the alkenyl group may have include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. The number of substituents that the alkenyl group may have is not particularly limited, but is preferably 3 or less.

In R _{11 to} R ₂₃ in the formulas (ETM-I) to (ETM-IV), examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms. And more preferably an alkoxy group having 1 to 4 carbon atoms. The alkoxy group may be any of a linear alkoxy group, a branched alkoxy group, a cyclic alkoxy group, or an alkoxy group obtained by combining these. Examples of the substituent that the alkoxy group may have include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a cyano group. The number of substituents that the alkoxy group may have is not particularly limited, but is preferably 3 or less.

In R _{11 to} R ₂₃ in the formulas (ETM-I) to (ETM-IV), examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, preferably 7 to 13 carbon atoms. And more preferably, an aralkyl group having 7 to 12 carbon atoms. Examples of the substituent that the aralkyl group may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, and a carbon atom. Examples thereof include an aliphatic acyl group having 2 or more and 4 or less, a benzoyl group, a phenoxy group, an alkoxycarbonyl group containing an alkoxy group having 1 to 4 carbon atoms, and a phenoxycarbonyl group. The number of substituents that the aralkyl group may have is not particularly limited, but is preferably 5 or less, and more preferably 3 or less.

In R _{11 to} R ₂₃ in the formulas (ETM-I) to (ETM-IV), the aromatic hydrocarbon group is formed by, for example, a phenyl group, two or three benzene rings being condensed. And groups formed by connecting two or three benzene rings by a single bond. The number of benzene rings contained in the aromatic hydrocarbon group is, for example, 1 or more and 3 or less, and preferably 1 or 2. Examples of the substituent that the aromatic hydrocarbon group may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, and a cyano group. And an aliphatic acyl group having 2 to 4 carbon atoms, a benzoyl group, a phenoxy group, an alkoxycarbonyl group containing an alkoxy group having 1 to 4 carbon atoms, and a phenoxycarbonyl group.

In R _{11 to} R ₂₃ in formulas (ETM-I) to (ETM-IV), the heterocyclic group is a 5-membered group containing one or more heteroatoms selected from the group consisting of N, S, and O; A 6-membered monocyclic heterocyclic group; a heterocyclic group in which such monocyclic rings are condensed; and a heterocyclic group in which such a monocyclic ring is condensed with a 5-membered or 6-membered hydrocarbon ring. It is done. When the heterocyclic group is a condensed ring, the number of rings contained in the condensed ring is preferably 3 or less. Examples of the substituent that the heterocyclic group may have include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, and carbon. Examples thereof include an aliphatic acyl group having 2 to 4 atoms, a benzoyl group, a phenoxy group, an alkoxycarbonyl group containing an alkoxy group having 1 to 4 carbon atoms, and a phenoxycarbonyl group.

In R ₂₃ in formula (ETM-IV), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

  Such an electron transport agent is used individually by 1 type or in combination of 2 or more types.

  In the positively charged single-layer type electrophotographic photosensitive member 1, the content of the electron transport agent is preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin. The following is more preferable.

(2-4) Binder resin Examples of the binder resin include a thermoplastic resin, a thermosetting resin, and a photocurable resin. Examples of the thermoplastic resin include polycarbonate resin, styrene resin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-acrylic acid copolymer, acrylic copolymer, Polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide resin, polyurethane resin, polyarylate resin, polysulfone resin , Diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, or polyester resin. Examples of the thermosetting resin include silicone resins, epoxy resins, phenol resins, urea resins, melamine resins, and other crosslinkable thermosetting resins. As photocurable resin, an epoxy acrylate resin or a urethane-acrylate copolymer resin is mentioned, for example.

  Among these resins, a polycarbonate resin is preferable because the single-layer type photosensitive layer 3 having an excellent balance of workability, mechanical properties, optical properties, and / or wear resistance can be obtained. Examples of the polycarbonate resin include bisphenol Z type polycarbonate resin, bisphenol ZC type polycarbonate resin, bisphenol C type polycarbonate resin, and bisphenol A type polycarbonate resin. More specifically, examples of the bisphenol Z-type polycarbonate resin include resins represented by the following formula.

  These binder resins may be used individually by 1 type, or may be used in combination of 2 or more type.

  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. If the molecular weight of the binder resin is too low, the abrasion resistance of the binder resin cannot be sufficiently increased, and the single-layer type photosensitive layer 3 is easily worn. On the other hand, if the molecular weight of the binder resin is too high, it becomes difficult to dissolve the binder resin in the solvent when the single-layer photosensitive layer 3 is formed, and the viscosity of the coating solution becomes too high, so that it is difficult to form the single-layer photosensitive layer 3. Tend to be.

(2-5) Additive In the photoreceptor 1 according to this embodiment, at least one of the single-layer type photosensitive layer 3, the intermediate layer 4, and the protective layer 5 does not adversely affect the electrophotographic characteristics. Various additives may be contained. 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.

(3) Method for Producing Positively Charged Single Layer Type Electrophotographic Photoreceptor Next, a method for producing the positively charged single layer type electrophotographic photoreceptor 1 will be described. The positively charged single-layer type electrophotographic photoreceptor 1 is manufactured by applying a coating solution for a single-layer type photosensitive layer 3 (hereinafter sometimes referred to as “coating solution”) onto the conductive substrate 2 and drying it. The The coating solution is produced by dissolving or dispersing a charge generator, a hole transport agent, an electron transport agent, a binder resin, and various additives as required in a solvent.

  The solvent contained in the coating solution is not particularly limited as long as each component contained in the coating solution can be dissolved or dispersed. Examples of the solvent include alcohols (for example, methanol, ethanol, isopropanol, or butanol), aliphatic hydrocarbons (for example, n-hexane, octane, or cyclohexane), 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), dimethylformal Hydrate, dimethylformamide, 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 1, it is preferable to use a solvent other than the halogenated hydrocarbon as the solvent.

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

  The coating 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 conductive substrate 2. 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.

  The thickness of the single-layer type photosensitive layer 3 of the positively charged single-layer type electrophotographic photosensitive member 1 is not particularly limited as long as it can sufficiently function as a single-layer type photosensitive layer. The thickness of the single-layer type photosensitive layer 3 is, for example, 5 μm or more and 100 μm or less, and preferably 10 μm or more and 50 μm or less.

The positively charged single layer type electrophotographic photosensitive member 1 is preferably used as an image carrier in an image forming apparatus including a contact-type charging unit that applies a DC voltage. The image forming apparatus having the charging of contact type, as compared with the image forming apparatus having the charging portion of the non-contact type has the advantage that the occurrence of adverse effects gas is small on the photosensitive member 1, such as ozone and NO _X . However, when the positively charged single-layer type electrophotographic photosensitive member 1 is used, the image forming apparatus including a charging unit that applies an alternating voltage causes the negative component (reverse polarity bias) to be applied to the photosensitive member 1. The stability of the surface potential may be reduced. Therefore, when the positively charged single layer type electrophotographic photosensitive member 1 is used in an image forming apparatus having a contact type charging unit, it is preferable to adopt a method of applying a DC voltage. Further, at the time of transfer, a negative component (a reverse polarity bias) is applied to the photosensitive member 1 through the transfer target. However, according to the photoconductor 1, it is possible to quickly move the charge having the opposite polarity, so that the potential on the photoconductor 1 can be stabilized. As a result, it is considered that the effect of suppressing the generation of the transfer memory is particularly exerted in the image forming apparatus including such a contact-type charging unit.

  The positively charged single layer type electrophotographic photosensitive member according to this embodiment has been described above with reference to FIG. The positively charged single layer type electrophotographic photosensitive member according to this embodiment can suppress the generation of a transfer memory while suppressing the crystallization of the surface of the photosensitive member. Therefore, the positively charged single layer type electrophotographic photosensitive member according to the present embodiment is suitably used as an image carrier in various image forming apparatuses.

[Second Embodiment: Image Forming Apparatus]
The second embodiment relates to an image forming apparatus. The image forming apparatus according to the present embodiment will be described below with reference to FIG. FIG. 2 is a schematic diagram showing a configuration of an image forming apparatus 6 of this embodiment including the positively charged single layer type electrophotographic photosensitive member 1 according to the first embodiment.

  The image forming apparatus 6 includes an image carrier, a charging unit, an exposure unit, a developing unit, and a transfer unit. The charging unit charges the surface of the image carrier. The exposure unit exposes the surface of the charged image carrier to form an electrostatic latent image on the surface of the image carrier. The developing unit develops the electrostatic latent image as a toner image. The transfer unit transfers the toner image from the image carrier to the transfer target. The image carrier is the positively charged single layer type electrophotographic photosensitive member 1 according to the first embodiment.

  The image forming apparatus 6 is not particularly limited as long as it is an electrophotographic image forming apparatus. The image forming apparatus 6 may be, for example, a monochrome image forming apparatus or a color image forming apparatus. In order to form toner images of different colors using different color toners, the image forming apparatus 6 of the present embodiment may be a tandem color image forming apparatus.

  Hereinafter, a tandem color image forming apparatus 6 will be described as an example. The tandem color image forming apparatus 6 includes a plurality of positively charged single layer type electrophotographic photoreceptors 1 (corresponding to image carriers) arranged in parallel in a predetermined direction, and a plurality of developing devices 29. The plurality of developing devices 29 are respectively disposed to face the photoreceptor 1. The plurality of developing devices 29 carry and carry toner on the surface of the developing device 29. Each of the plurality of developing devices 29 includes a developing roller. The developing roller supplies the conveyed toner to the surface of the corresponding photoreceptor 1. The positively charged single-layer type electrophotographic photosensitive member according to the first embodiment containing the triphenylamine derivative (1) can be used as the photosensitive member 1.

  As shown in FIG. 2, the image forming apparatus 6 has a box-shaped device housing 7. In the device housing 7, a paper feeding unit 8, an image forming unit 9, and a fixing unit 10 are provided. The paper feed unit 8 feeds the paper P. The image forming unit 9 transfers the toner image based on the image data to the paper P while conveying the paper P fed from the paper feeding unit 8. The fixing unit 10 fixes the unfixed toner image transferred on the paper P by the image forming unit 9 to the paper P. Further, a paper discharge unit 11 is provided on the upper surface of the device housing 7. The paper discharge unit 11 discharges the paper P fixed by the fixing unit 10.

  The paper supply unit 8 includes a paper supply cassette 12, a pickup roller 13, paper supply rollers 14, 15 and 16, and a registration roller pair 17. The paper feed cassette 12 is provided so as to be detachable from the device housing 7. Various sizes of paper P are stored in the paper feed cassette 12. The pickup roller 13 is provided at the upper left position of the paper feed cassette 12. The pickup roller 13 takes out the sheets P stored in the sheet feeding cassette 12 one by one. The paper feed rollers 14, 15 and 16 convey the paper P taken out by the pickup roller 13. The registration roller pair 17 temporarily supplies the paper P conveyed by the paper feed rollers 14, 15, and 16 to the image forming unit 9 at a predetermined timing.

  The paper feed unit 8 further includes a manual feed tray (not shown) and a pickup roller 18. The manual feed tray is attached to the left side surface of the device housing 7. The pickup roller 18 takes out the paper P placed on the manual feed tray. The paper P taken out by the pickup roller 18 is transported by the paper feeding rollers 14, 15 and 16, and is supplied to the image forming unit 9 by the registration roller pair 17 at a predetermined timing.

  The image forming unit 9 includes an image forming unit 19, an intermediate transfer belt 20, and a secondary transfer roller 21. A toner image is primarily transferred onto the intermediate transfer belt 20 by the image forming unit 19 on the surface of the intermediate transfer belt 20 (contact surface with the primary transfer roller 33). The toner image to be primarily transferred is formed based on image data transmitted from a host device such as a computer. The secondary transfer roller 21 secondarily transfers the toner image on the intermediate transfer belt 20 onto the paper P fed from the paper feed cassette 12.

  The image forming unit 19 includes a magenta toner supply unit 25, a cyan toner supply unit 24, a yellow toner supply unit 23, and a black toner supply unit 22 from the upstream side (right side in FIG. 2) to the downstream side. Are sequentially arranged. In each of the units 22, 23, 24, and 25, a photosensitive member 1 (corresponding to an image carrier) is disposed at the center position of each unit. The photoreceptor 1 is disposed so as to be rotatable in the direction of an arrow (clockwise).

  Around each photoconductor 1, there are a charging device 27 (corresponding to a charging portion), an exposure device 28 (corresponding to an exposure portion), a developing device 29 (corresponding to a developing portion), a cleaning device (not shown), and a removal device. Electric appliances (not shown) are arranged in order from the upstream side in the rotation direction of each photoconductor 1. As the photoreceptor 1, the positively charged single layer type electrophotographic photoreceptor 1 according to the first embodiment is used.

  The charging device 27 (corresponding to a charging unit) charges the surface of the photoreceptor 1 (corresponding to an image carrier). Specifically, the charging device 27 uniformly charges the peripheral surface of the photoreceptor 1 rotated in the direction of the arrow. The charging device 27 is not particularly limited as long as the peripheral surface of the photoreceptor 1 can be uniformly charged. The charging device 27 may be a non-contact charging device or a contact charging device. Examples of the charging device 27 include a corona charging device, a charging roller, and a charging brush. As the charging device 27, a contact-type charging device (specifically, a charging roller or a charging brush) is preferable, and a charging roller is more preferable. By using the contact-type charging device 27, discharge of active gas (for example, ozone and nitrogen oxide) generated from the charging device 27 can be suppressed. As a result, it is possible to suppress the deterioration of the single-layer type photosensitive layer 3 due to the active gas and to achieve a design in consideration of the office environment.

  When the charging device 27 includes a contact-type charging roller, the charging roller charges the peripheral surface (surface) of the photoconductor 1 while being in contact with the photoconductor 1. As such a charging roller, for example, a charging roller that rotates depending on the rotation of the photosensitive member 1 while being in contact with the photosensitive member 1 can be used. Moreover, as a charging roller, the charging roller by which the surface part was comprised with resin at least is mentioned, for example. More specifically, as the charging rotor, for example, there is a charging roller including a core metal rotatably supported, a resin layer formed on the core metal, and a voltage application unit that applies a voltage to the core metal. Can be mentioned. The charging device 27 equipped with such a charging roller can charge the surface of the photoreceptor 1 that is in contact with the resin through the resin layer when the voltage application unit applies a voltage to the cored bar.

  The voltage applied by the charging device 27 is not particularly limited. However, it is preferable that the charging device 27 applies only the DC voltage, rather than when the charging device 27 applies an AC voltage or when a superimposed voltage obtained by superimposing the AC voltage on the DC voltage is applied. This is because when the charging device 27 applies only a DC voltage, the wear amount of the single-layer type photosensitive layer 3 tends to decrease. As a result, a suitable image can be formed. The DC voltage applied to the photoreceptor 1 by the charging device 27 is preferably 1000 V or more and 2000 V or less, more preferably 1200 V or more and 1800 V or less, and particularly preferably 1400 V or more and 1600 V or less.

  The resin constituting the resin layer of the charging roller is not particularly limited as long as the peripheral surface of the photoreceptor 1 can be charged satisfactorily. Specific examples of the resin constituting the resin layer include a silicone resin, a urethane resin, and a silicone-modified resin. The resin layer may contain an inorganic filler.

  The exposure device 28 (corresponding to an exposure unit) is a so-called laser scanning unit. The exposure device 28 exposes the surface of the charged photoconductor 1 (corresponding to an image carrier) to form an electrostatic latent image on the surface of the photoconductor 1. Specifically, the exposure device 28 irradiates the peripheral surface (surface) of the photoreceptor 1 uniformly charged by the charging device 27 with laser light based on image data input from a host device such as a personal computer. . Thereby, an electrostatic latent image based on the image data is formed on the peripheral surface (front surface) of the photoreceptor 1.

  The developing device 29 (corresponding to a developing unit) develops the electrostatic latent image as a toner image. Specifically, the developing device 29 supplies toner to the peripheral surface of the photoreceptor 1 on which the electrostatic latent image is formed, and forms a toner image based on the image data. Then, the formed toner image is primarily transferred to the intermediate transfer belt 20. The cleaning device cleans the toner remaining on the peripheral surface of the photoreceptor 1 after the primary transfer of the toner image to the intermediate transfer belt 20 is completed. The static eliminator neutralizes the peripheral surface of the photoreceptor 1 after the primary transfer of the toner image to the intermediate transfer belt 20 is completed. The peripheral surface of the photoreceptor 1 cleaned and discharged by the cleaning device and the charge eliminator is sent to the charging device 27 and newly charged.

  The intermediate transfer belt 20 is an endless belt rotating body. The intermediate transfer belt 20 is stretched around a driving roller 30, a driven roller 31, a backup roller 32, and a plurality of primary transfer rollers 33. The intermediate transfer belt 20 is installed such that the circumferential surfaces of the plurality of photoreceptors 1 are in contact with the surface (contact surface) of the intermediate transfer belt 20.

  Further, the intermediate transfer belt 20 is pressed against the photoconductor 1 by a primary transfer roller 33 disposed to face each photoconductor 1. In the pressed state, the intermediate transfer belt 20 rotates endlessly by a plurality of primary transfer rollers 33. The driving roller 30 is rotationally driven by a driving source such as a stepping motor, and gives a driving force for rotating the intermediate transfer belt 20 endlessly. The driven roller 31, the backup roller 32, and the plurality of primary transfer rollers 33 are rotatably provided. The driven roller 31, the backup roller 32, and the primary transfer roller 33 rotate following the endless rotation of the intermediate transfer belt 20 by the driving roller 30. The driven roller 31, the backup roller 32, and the primary transfer roller 33 are driven to rotate via the intermediate transfer belt 20 according to the main rotation of the driving roller 30 and support the intermediate transfer belt 20.

  The transfer unit transfers the toner image from the image carrier to the transfer target. Specifically, the primary transfer roller 33 applies a primary transfer bias (specifically, a bias having a polarity opposite to the charging polarity of the toner) to the intermediate transfer belt 20 (corresponding to a transfer target). As a result, the toner image formed on each photoconductor 1 is rotated between the photoconductor 1 and the primary transfer roller 33 in the direction of the arrow (counterclockwise) by driving the drive roller 30. 20 is sequentially transferred (primary transfer).

  The secondary transfer roller 21 applies a secondary transfer bias (specifically, a bias having a polarity opposite to that of the toner image) to the paper P. As a result, the toner image primarily transferred onto the intermediate transfer belt 20 is transferred onto the paper P between the secondary transfer roller 21 and the backup roller 32. As a result, an unfixed toner image is transferred onto the paper P.

  Here, in the present embodiment, the image forming apparatus 6 adopting the intermediate transfer method using the intermediate transfer belt 20 is described. However, the positively charged single layer type electrophotographic photoreceptor 1 according to the first embodiment can be more suitably used in an image forming apparatus that employs a direct transfer system. The direct transfer method is a method in which the toner image developed on the surface of the photosensitive drum is directly transferred to the paper P conveyed by the transfer belt. In an image forming apparatus that employs the direct transfer method, foreign matter caused by the paper P tends to adhere to the surface of the photosensitive drum. Therefore, the generated deposit may cause a decrease in charge. Due to the influence of such a decrease in charging, a transfer memory is likely to occur in an image forming apparatus that employs the direct transfer method. However, the provision of the positively charged single-layer type electrophotographic photosensitive member 1 according to the first embodiment effectively suppresses the generation of the transfer memory even in the image forming apparatus adopting the direct transfer system that easily causes the transfer memory. be able to. An image forming apparatus that employs the direct transfer method will be described later with reference to FIG.

  The fixing unit 10 fixes the unfixed toner image transferred to the paper P by the image forming unit 9. The fixing unit 10 includes a heating roller 34 and a pressure roller 35. The heating roller 34 is heated by an energized heating element. The pressure roller 35 is disposed to face the heating roller 34, and the circumferential surface of the pressure roller 35 is pressed against the circumferential surface of the heating roller 34.

  The transfer image transferred to the paper P by the secondary transfer roller 21 in the image forming unit 9 is fixed to the paper P by a fixing process by heating when the paper P passes between the heating roller 34 and the pressure roller 35. The Then, the paper P subjected to the fixing process is discharged to the paper discharge unit 11. In addition, a plurality of transport rollers 36 are disposed at appropriate positions between the fixing unit 10 and the paper discharge unit 11.

  The paper discharge unit 11 is formed by recessing the top of the device housing 7. A paper discharge tray 37 that receives the discharged paper P is provided at the bottom of the recessed portion. The image forming apparatus according to the present embodiment has been described above with reference to FIG.

  Hereinafter, with reference to FIG. 3, an image forming apparatus employing a direct transfer method according to another aspect of the present embodiment will be described. In FIG. 3, the same reference numerals are used for the elements corresponding to those in FIG. As shown in FIG. 3, the transfer belt 40 is an endless belt-like rotating body. The transfer belt 40 is stretched around a driving roller 30, a driven roller 31, a backup roller 32, and a plurality of transfer rollers 41. The transfer belt 40 is installed so that the circumferential surface of each photoconductor 1 is in contact with the surface (contact surface) of the transfer belt 40. The transfer belt 40 is pressed against the photoconductor 1 by each transfer roller 41 disposed to face each photoconductor 1. In the pressed state, the transfer belt 40 is rotated endlessly by the plurality of rollers 30, 31, 32, and 41. The driving roller 30 is rotationally driven by a driving source such as a stepping motor, and gives a driving force for rotating the transfer belt 40 endlessly. The driven roller 31, the backup roller 32, and the transfer roller 41 are rotatably provided. With the endless rotation of the transfer belt 40 by the driving roller 30, the driven roller 31, the backup roller 32, and the plurality of transfer rollers 41 are driven to rotate. These rollers 31, 32 and 41 are driven to rotate and support the transfer belt 40. The paper P supplied from the registration roller pair 17 is sucked onto the transfer belt 40 by the suction roller 42. The sheet P adsorbed on the transfer belt 40 passes between each photoconductor 1 and the corresponding transfer roller 41 as the transfer belt 40 rotates.

  Each transfer roller 41 applies a transfer bias (a polarity opposite to the charging polarity of the toner) to the paper P adsorbed on the transfer belt 40. As a result, the toner image formed on the photoconductor 1 is transferred onto the paper P between each photoconductor 1 and the corresponding transfer roller 41. The transfer belt 40 circulates in the arrow (clockwise) direction by driving the driving roller 30. Accordingly, the paper P sucked on the transfer belt 40 sequentially passes between each photoconductor 1 and the corresponding transfer roller 41. When passing, the toner images of the corresponding colors formed on the respective photoreceptors 1 are sequentially transferred onto the paper P in the overcoated state. Thereafter, each photoconductor 1 further rotates and proceeds to the next process. The image forming apparatus that employs the direct transfer method according to another aspect of the present embodiment has been described above with reference to FIG.

  As described with reference to FIGS. 2 and 3, the image forming apparatus according to the present embodiment is a positively charged single layer type electrophotographic photosensitive member according to the first embodiment that can suppress a transfer memory as an image carrier. Has a body. By including such a positively charged single-layer type electrophotographic photosensitive member, the image forming apparatus according to the present embodiment can suppress the occurrence of image defects.

  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 triphenylamine derivative [synthesis of triphenylamine derivative (HT-1)]
First, the reaction shown in the following reaction formula (R-4) was performed.

Specifically, 6.8 g (0.05 mol) of the aniline derivative represented by the formula (13) and 5.6 g (0 g) of dichlorobiphenyl represented by the formula (14) were added to a 2 L two-necked flask. 0.025 mol), 0.0662 g (0.000189 mol) of tricyclohexylphosphine (Pcy3), 0.0864 g (0.0000944 mol) of tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) ) And 7.68 g (0.08 mol) of sodium-tert-butoxide (t-BuONa). Furthermore, 500 mL of distilled o-xylene was added. Then, argon gas substitution was performed and it reacted for 5 hours, stirring at 120 degreeC.

  Next, the reaction liquid (solution containing the reaction product and o-xylene) was cooled to room temperature to obtain an organic phase. The obtained organic phase was washed three times with ion exchange water. Further, the organic phase was dried and adsorbed using anhydrous sodium sulfate and activated clay. Thereafter, o-xylene was distilled off under reduced pressure to obtain a residue.

  The resulting residue was purified using column chromatography (developing solvent: a mixed solvent of chloroform and hexane) to obtain 7.5 g (yield: 71%) of the biphenylamine derivative represented by the formula (15). .

Subsequently, reaction as shown to following reaction formula (R-5) was performed.

  Specifically, 16.1 g (0.1 mol) of the benzene derivative represented by the formula (16) and 25 g (0.15 mol) of triethyl phosphite were charged into a 200 mL flask. This was stirred for 8 hours while heating at 180 ° C. Subsequently, after cooling to room temperature, excess triethyl phosphite was distilled off under reduced pressure to obtain 24.1 g (yield: 92%) of the phosphonate derivative (white liquid) represented by the formula (17).

  Then, 13.0 g (0.05 mol) of the phosphonate derivative represented by the formula (17) was put into a 500 mL two-necked flask, and argon gas substitution was performed. To this, 100 mL of dried tetrahydrofuran (THF) and 9.3 g (0.05 mol) of a methanol solution of sodium methoxide (concentration: 28% by mass) were added and stirred at 0 ° C. for 30 minutes. A mixed solution prepared by dissolving 7.0 g (0.05 mol) of a cinnamaldehyde derivative represented by the formula (18) in 300 mL of dry THF was added to the reaction solution, and the mixture was stirred at room temperature for 12 hours.

  Thereafter, the reaction solution was poured into ion-exchanged water and extracted with toluene to obtain an organic phase (toluene phase). The obtained organic phase was washed 5 times with ion exchange water. Subsequently, after drying an organic phase with anhydrous sodium sulfate, the solvent was distilled off to obtain a residue. Thereafter, the residue was purified by recrystallization with a solvent (a mixed solvent of 20 mL of toluene and 100 mL of methanol), and 10.22 g (yield: 80%) of the diphenylbutadiene derivative (white crystals) represented by the formula (19) Got.

Next, a reaction as shown in the following reaction formula (R-6) was performed to synthesize a triphenylamine derivative (HT-1) as a final target product.

  Specifically, 10.5 g (0.025 mol) of a biphenylamine derivative represented by the formula (15), 0.0662 g (0.000189 mol) of tricyclohexylphosphine, and tris (dibenzylideneacetone) are added to a three-necked flask. ) Dipalladium (0) 0.0864 g (0.0000944 mol), sodium-tert-butoxide (t-BuONa) 7.68 g (0.08 mol), and diphenylbutadiene derivative 11 represented by formula (19) 0.0 g (0.05 mol) was added. Furthermore, 500 mL of distilled o-xylene was added. Then, argon gas substitution was performed and it reacted for 5 hours, stirring at 120 degreeC.

  Subsequently, the reaction liquid was cooled to room temperature to obtain an organic phase. The obtained organic phase was washed three times with ion-exchanged water, and further dried and adsorbed using anhydrous sodium sulfate and activated clay. Thereafter, o-xylene was distilled off under reduced pressure to obtain a residue.

  The obtained residue was purified using column chromatography (developing solvent: mixed solvent of chloroform and hexane) to obtain 13.5 g of a triphenylamine derivative (HT-1) (yield: 65%).

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

[Synthesis of Triphenylamine Derivative (HT-2)]
Reaction similar to reaction shown by Reaction formula (R-4) was performed, and the biphenylamine derivative represented by Formula (15) was obtained. The yield was 71%. Next, the cinnamaldehyde derivative represented by the formula (18) is changed to a cinnamaldehyde derivative represented by the formula (20), and is represented by the following reaction formula (R-7) instead of the reaction formula (R-5). A diphenylbutadiene derivative represented by the formula (21) was obtained. The yield was 70%.

Next, in place of the diphenylbutadiene derivative represented by the formula (19), the diphenylbutadiene derivative represented by the formula (21) is used, and instead of the reaction formula (R-6), the following reaction formula (R-8) is used. The reaction as shown was performed to synthesize a triphenylamine derivative (HT-2). The yield was 65%. The ¹ H-NMR spectrum of the triphenylamine derivative (HT-2) is shown in FIG.

  In addition, in the synthesis | combination of a triphenylamine derivative (HT-2) and the synthesis | combination of the (HT-3)-triphenylamine derivative (HT-8) mentioned later, those molar scales are triphenylamine derivatives (HT-1). The blending amount of the material was adjusted so as to be equal to the molar scale in the synthesis of).

[Synthesis of triphenylamine derivative (HT-3)]
Instead of the aniline derivative represented by the formula (13), an aniline derivative represented by the formula (23) is used, and instead of the reaction formula (R-4), the following reaction formula (R-9) is used. The reaction was performed to obtain a biphenylamine derivative represented by the formula (24). The yield was 70%.

Next, in place of the biphenylamine derivative represented by the formula (15), the biphenylamine derivative represented by the formula (24) is used, and instead of the reaction formula (R-6), the following reaction formula (R-10) is used. The reaction as shown was performed to synthesize a triphenylamine derivative (HT-3). The yield was 70%. The ¹ H-NMR spectrum of the triphenylamine derivative (HT-3) is shown in FIG.

[Synthesis of Triphenylamine Derivative (HT-4)]
Instead of the aniline derivative represented by the formula (13), an aniline derivative represented by the formula (25) is used, and instead of the reaction formula (R-4), the following reaction formula (R-11) is used. Reaction was performed and the biphenylamine derivative represented by Formula (26) was obtained. The yield was 50%.

Subsequently, instead of the reaction formula (R-6), a reaction represented by the following reaction formula (R-12) was performed to synthesize a triphenylamine derivative (HT-4). In the reaction formula (R-12), a biphenylamine derivative represented by the formula (26) was used instead of the biphenylamine derivative represented by the formula (15). Moreover, it replaced with the diphenyl butadiene derivative represented by Formula (19), and the diphenyl butadiene derivative represented by Formula (21) was used. The yield of the obtained triphenylamine derivative (HT-4) was 65%. A ¹ H-NMR spectrum of the triphenylamine derivative (HT-4) is shown in FIG.

[Synthesis of Triphenylamine Derivative (HT-5)]
The cinnamaldehyde derivative represented by the following (27) is used instead of the cinnamaldehyde represented by the formula (18), and the reaction formula (R-13) is used instead of the reaction formula (R-5). Thus, a diphenylbutadiene derivative represented by the formula (28) was obtained. The yield was 65%.

Next, a diphenylbutadiene derivative represented by the formula (28) is used instead of the diphenylbutadiene derivative represented by the formula (19), and the reaction formula (R-14) is used instead of the reaction formula (R-6). As described above, a triphenylamine derivative (HT-5) was synthesized. The yield was 65%. The ¹ H-NMR spectrum of the triphenylamine derivative (HT-5) is shown in FIG.

[Synthesis of Triphenylamine Derivative (HT-6)]
Instead of cinnamaldehyde represented by formula (18), a cinnamaldehyde derivative represented by formula (29) is used, and instead of reaction formula (R-5), it is represented by the following reaction formula (R-15). Thus, a diphenylbutadiene derivative represented by the formula (30) was obtained. The yield was 50%.

  Subsequently, instead of the reaction formula (R-6), a reaction represented by the following reaction formula (R-16) was performed to synthesize a triphenylamine derivative (HT-6). In the reaction formula (R-16), a biphenylamine derivative represented by the formula (24) was used instead of the biphenylamine derivative represented by the formula (15). Moreover, it replaced with the diphenyl butadiene derivative represented by Formula (19), and used the diphenyl butadiene derivative represented by Formula (30). The yield of the obtained triphenylamine derivative (HT-6) was 60%.

[Synthesis of Triphenylamine Derivative (HT-7)]
Instead of the aniline derivative represented by the formula (13), an aniline derivative represented by the formula (31) is used, and instead of the reaction formula (R-4), the following reaction formula (R-17) is used. Reaction was performed and the biphenylamine derivative represented by Formula (32) was obtained. The yield was 65%.

  Next, the biphenylamine derivative represented by the formula (32) is used instead of the biphenylamine derivative represented by the formula (15), and the reaction formula (R-18) is used instead of the reaction formula (R-6). As described above, a triphenylamine derivative (HT-7) was synthesized. The yield was 70%.

[Synthesis of Triphenylamine Derivative (HT-8)]
Instead of the aniline derivative represented by the formula (13), the aniline derivative represented by the formula (33) is used, and instead of the reaction formula (R-4), the following reaction formula (R-19) is used. Reaction was performed and the biphenylamine derivative represented by Formula (34) was obtained. The yield was 50%.

  Next, a biphenylamine derivative represented by the formula (34) is used instead of the biphenylamine derivative represented by the formula (15), and the reaction formula (R-20) is used instead of the reaction formula (R-6). Thus, a triphenylamine derivative (HT-8) was synthesized. The yield was 65%.

(2) Production of positively charged single layer type electrophotographic photosensitive member [photosensitive member (A-1)]
In the container, an X-type metal-free phthalocyanine (5 parts by mass) as a charge generating agent, a triphenylamine derivative (HT-1) (50 parts by mass) as a hole transporting agent, and the following electron transporting agent (35 Part by mass), the following binder resin (100 parts by mass), and tetrahydrofuran (800 parts by mass) as a solvent were added. The contents were mixed with a ball mill for 50 hours, and the material was dispersed in a solvent to obtain a single-layer type photosensitive layer coating solution. The electron transfer agent is represented by the following formula (wherein R ₁₁ ′ and R ₁₃ ′ each represent a methyl group. R ₁₂ ′ and R ₁₄ ′ each represent a tert-butyl group). The electron transport agent (ETM-1) was used.

  As the binder resin, a resin represented by the following formula was used.

  Next, the obtained coating solution was applied to the surface of an aluminum drum-shaped support (diameter 30 mm, total length 238.5 mm) as a conductive substrate using a dip coating method. Thereafter, heat treatment (hot air drying) was performed at 100 ° C. for 40 minutes to remove tetrahydrofuran from the coating film. As a result, a single-layer type photosensitive layer (thickness 30 μm) was formed to obtain a photoreceptor (A-1) which is a positively charged single-layer type electrophotographic photoreceptor.

[Photoreceptor (A-2)]
The photoconductor (A-2) was prepared in the same manner as in the production of the photoconductor (A-1) except that the following electron transfer agent (ETM-2) was used instead of the electron transfer agent (ETM-1). Manufactured.

In the above formula, R ₁₅ ′ represents a methyl group. R ₁₆ ′ represents a methyl group. R ₁₇ ′ represents a tert-butyl group. R ₁₈ ′ represents a tert-butyl group.

[Photoreceptor (A-3)]
The photoconductor (A-3) was prepared in the same manner as in the production of the photoconductor (A-1) except that the following electron transfer agent (ETM-3) was used instead of the electron transfer agent (ETM-1). Manufactured.

In the above formula, R ₁₉ ′ represents a 1,1-dimethylpropyl group. R ₂₀ ′ represents a 1,1-dimethylpropyl group.

[Photoreceptor (A-4)]
The photoconductor (A-4) was prepared in the same manner as in the production of the photoconductor (A-1) except that the following electron transfer agent (ETM-4) was used instead of the electron transfer agent (ETM-1). Manufactured.

In the above formula, R ₂₁ ′ represents a tert-butyl group. R ₂₂ ′ represents a tert-butyl group. R ₂₃ ′ represents a chlorine atom located in the para position with respect to the nitrogen atom.

[Photoreceptor (A-5)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-2) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-5) was produced.

[Photosensitive member (A-6)]
As a hole transport agent, a triphenylamine derivative (HT-2) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-6) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-7)]
As the hole transport agent, a triphenylamine derivative (HT-2) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-7) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (A-8)]
As the hole transport agent, a triphenylamine derivative (HT-2) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoconductor (A-8) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-9)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-3) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-9) was produced.

[Photosensitive member (A-10)]
As the hole transport agent, a triphenylamine derivative (HT-3) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-10) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (A-11)]
As the hole transport agent, a triphenylamine derivative (HT-3) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-11) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-12)]
As a hole transport agent, a triphenylamine derivative (HT-3) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoconductor (A-12) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-13)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-4) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-13) was produced.

[Photosensitive member (A-14)]
As a hole transport agent, a triphenylamine derivative (HT-4) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoreceptor (A-14) was produced in the same manner as in the production of the photoreceptor (A-1), except that it was used.

[Photosensitive member (A-15)]
As the hole transport agent, a triphenylamine derivative (HT-4) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-15) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-16)]
As the hole transport agent, a triphenylamine derivative (HT-4) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoconductor (A-16) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-17)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-5) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-17) was produced.

[Photosensitive member (A-18)]
As the hole transport agent, a triphenylamine derivative (HT-5) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-18) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-19)]
As a hole transport agent, a triphenylamine derivative (HT-5) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-19) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-20)]
As the hole transport agent, a triphenylamine derivative (HT-5) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoreceptor (A-20) was produced in the same manner as in the production of the photoreceptor (A-1) except that it was used.

[Photosensitive member (A-21)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-6) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-21) was manufactured.

[Photosensitive member (A-22)]
As a hole transport agent, a triphenylamine derivative (HT-6) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-22) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-23)]
As the hole transport agent, a triphenylamine derivative (HT-6) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoreceptor (A-23) was produced in the same manner as in the production of the photoreceptor (A-1) except that it was used.

[Photosensitive member (A-24)]
As the hole transport agent, a triphenylamine derivative (HT-6) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoconductor (A-24) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-25)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-7) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-25) was produced.

[Photosensitive member (A-26)]
As a hole transport agent, a triphenylamine derivative (HT-7) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-26) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-27)]
As the hole transport agent, a triphenylamine derivative (HT-7) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-27) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (A-28)]
As the hole transport agent, a triphenylamine derivative (HT-7) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoreceptor (A-28) was produced in the same manner as in the production of the photoreceptor (A-1) except that it was used.

[Photosensitive member (A-29)]
The photoconductor was prepared in the same manner as in the production of the photoconductor (A-1) except that the triphenylamine derivative (HT-8) was used instead of the triphenylamine derivative (HT-1) as the hole transport agent. (A-29) was produced.

[Photosensitive member (A-30)]
As the hole transport agent, a triphenylamine derivative (HT-8) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (A-30) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-31)]
As the hole transport agent, a triphenylamine derivative (HT-8) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (A-31) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (A-32)]
As a hole transport agent, a triphenylamine derivative (HT-8) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoreceptor (A-32) was produced in the same manner as in the production of the photoreceptor (A-1) except that it was used.

[Photosensitive member (A-33)]
A photoconductor (A-33) was produced in the same manner as the photoconductor (A-1) except that titanyl phthalocyanine was used instead of X-type metal-free phthalocyanine as the charge generating agent.

[Photoreceptor (B-1)]
Except for using the following triphenylamine derivative (HT-A) in place of the triphenylamine derivative (HT-1) as a hole transporting agent, the same procedure as in the production of the photoreceptor (A-1) was used. A photoreceptor (B-1) was produced.

[Photoreceptor (B-2)]
As a hole transport agent, a triphenylamine derivative (HT-A) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (B-2) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (B-3)]
As the hole transport agent, a triphenylamine derivative (HT-A) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (B-3) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photosensitive member (B-4)]
As a hole transport agent, a triphenylamine derivative (HT-A) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoconductor (B-4) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (B-5)]
Except for using the following triphenylamine derivative (HT-B) in place of the triphenylamine derivative (HT-1) as a hole transporting agent, the same procedure as in the production of the photoreceptor (A-1) was used. A photoreceptor (B-5) was produced.

[Photoreceptor (B-6)]
As the hole transport agent, a triphenylamine derivative (HT-B) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-2) is used instead of the electron transport agent (ETM-1). A photoconductor (B-6) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (B-7)]
As the hole transport agent, a triphenylamine derivative (HT-B) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-3) is used instead of the electron transport agent (ETM-1). A photoconductor (B-7) was produced in the same manner as in the production of the photoconductor (A-1) except that it was used.

[Photoreceptor (B-8)]
As a hole transport agent, a triphenylamine derivative (HT-B) is used instead of the triphenylamine derivative (HT-1), and an electron transport agent (ETM-4) is used instead of the electron transport agent (ETM-1). A photoreceptor (B-8) was produced in the same manner as in the production of the photoreceptor (A-1) except that it was used.

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

(3) Appearance Evaluation of Photoreceptor The entire surface of any one of the photoreceptors (A-1) to (A-33) and the photoreceptors (B-1) to (B-8) is used with an optical microscope. Were observed to confirm the presence of crystallized portions. The appearance of the photoreceptor was evaluated according to the following criteria.
○ (good): no crystallized portion is observed.
X (Poor): A crystallized portion is observed.

(4) Transfer memory potential Any of the photoconductors (A-1) to (A-33) and the photoconductors (B-1) to (B-8) can be used as a color printer (FS-C5250DN, Kyocera Document). (Solutions Corporation). Conditions were set so that the surface potential of the photoreceptor was 600V. A DC voltage was applied to the charging roller of the charging device to charge the photoreceptor. A charging rotor that applies a DC voltage was used as a charging unit of the color printer. As the charging roller, a roller made of a chargeable rubber (specifically, a roller made of a material in which conductive carbon is dispersed in epichlorohydrin resin) was used. An intermediate transfer method was adopted as the transfer method. Specifically, a method was adopted in which the toner image on the photosensitive drum was transferred to a transfer belt, and then the toner image was transferred to a paper medium. Using this color printer, the difference between the potential at the white paper portion before application of the transfer bias and the potential at the white paper portion when the transfer bias was applied was measured. The measured potential difference was evaluated as a transfer memory.

(5) Image evaluation One of the photoconductors (A-1) to (A-33) and the photoconductors (B-1) to (B-8) is replaced with a color printer (FS-C5250DN, Kyocera Document Solutions). (Made by Co., Ltd.). For the color printer, the charging unit and the transfer method used in the evaluation of the transfer memory potential described above were adopted. Using this color printer, after durability printing for 1 hour, an evaluation image was printed. The printed evaluation image was observed for occurrence of image defects. Based on the presence or absence of image defects, images were evaluated according to the following criteria. ◎ (very good) and ○ (good) were evaluated as acceptable.
A (very good): Image defect is not observed.
○ (Good): A white-out portion having a side of 10 mm is observed as a ghost in the halftone portion.
Δ (Normal): A white-out portion having a side of 10 mm is observed as a ghost in the halftone portion. Further, although it cannot be clearly read, an alphabet-shaped white spot with a side of 3 mm is observed as a ghost.
X (with defects): Alphabet-shaped white spots with a side of 3 mm can be clearly read as ghosts.

For each of the photoreceptors (A-1) to (A-33) and (B-1) to (B-8), a charge generating agent, a hole transporting agent and an electron transporting agent contained in the single-layer type photosensitive layer Tables 1 and 2 show the results of various evaluations. In Tables 1 and 2, “X—H ₂ Pc” and “TiOPc” represent “X-type metal-free phthalocyanine” and “titanyl phthalocyanine”, respectively.

  As is clear from Tables 1 and 2, a positively charged single layer type electrophotographic photosensitive member containing a hole transport agent containing triphenylamine derivatives (HT-1) to (HT-8) in a single layer type photosensitive layer. In the bodies (A-1) to (A-33), not only the crystallization of the single-layer type photosensitive layer was suppressed, but also the generation of transfer memory was suppressed. As a result, the occurrence of image defects such as ghosts is effectively suppressed.

  On the other hand, positively charged single layer type electrophotographic photoreceptors (B-1) to (B) containing a hole transport agent containing a triphenylamine derivative (HT-A) or (HT-B) in a single layer type photosensitive layer. In −8), the difference between the potential in the blank portion before application of the transfer bias and the potential in the blank portion when the transfer bias was applied tended to increase. As a result, transfer memory was generated, and the occurrence of image defects such as ghost was confirmed.

  The positively charged single layer type electrophotographic photosensitive member according to the present invention can be suitably used for an image forming apparatus.

DESCRIPTION OF SYMBOLS 1 Positively charged single layer type electrophotographic photosensitive member 2 Conductive substrate 3 Single layer type photosensitive layer 4 Intermediate layer 5 Protective layer 6 Image forming apparatus 7 Equipment housing 8 Paper feed portion 9 Image forming portion 10 Fixing portion 11 Paper discharge portion 12 Feed Paper cassette 13 Pickup roller 14 Paper feed roller 15 Paper feed roller 16 Paper feed roller 17 Registration roller pair 18 Pickup roller 19 Image forming unit 20 Intermediate transfer belt 21 Secondary transfer roller 22 Black toner supply unit 23 Yellow toner supply unit 24 Cyan toner supply unit 25 Magenta toner supply unit 27 Charging device 28 Exposure device 29 Development device 30 Driving roller 31 Driven roller 32 Backup roller 33 Primary transfer roller 34 Heating roller 35 Pressure roller 36 Transport roller 37 Paper discharge tray 40 Transfer belt 4 1 Transfer roller 42 Adsorption roller

Claims (7)

A positively charged single layer type electrophotographic photosensitive member comprising a conductive substrate and a single layer type photosensitive layer disposed on the conductive substrate,
The single-layer type photosensitive layer includes at least a charge generator, a hole transport agent, an electron transport agent, and a binder resin,
The positively charged single-layer type electrophotographic photosensitive member, wherein the hole transport agent includes a triphenylamine derivative represented by the following general formula (1).

In the general formula (1),
R _{1 to} R ₇ are independently the same or different and each has a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and the number of carbon atoms which may have a substituent. Selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent;
k, l, m, n, o, and p each represent an integer of 0 or more and 4 or less,
When k, l, m, n, o, or p represents an integer of 2 or more, a plurality of corresponding R ₃ , R ₄ , R ₅ , R ₅ , R ₆ , or R present in the same aromatic ring Each of ₇ may be the same or different. _2. The positively charged single-layer electrophotographic photosensitive member according to claim 1, wherein R ₁ and R ₂ in the general formula (1) are each an alkyl group having 1 to 6 carbon atoms. In the general formula (1),
R _{1 to} R ₄ are independently the same or different and each is an alkyl group having 1 to 6 carbon atoms,
3. The positively charged single layer type electrophotographic photosensitive member according to claim 1, wherein k and l represent an integer of 1.   The positively charged single layer type electrophotographic photosensitive member according to any one of claims 1 to 3, which is used as an image carrier in an image forming apparatus including a contact-type charging unit that applies a DC voltage. An image carrier;
A charging unit that charges the surface of the image carrier;
An exposure unit that exposes the surface of the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
A developing unit for developing the electrostatic latent image as a toner image;
A transfer unit that transfers the toner image from the image carrier to a transfer target;
An image forming apparatus, wherein the image carrier is the positively charged single layer type electrophotographic photosensitive member according to claim 1.   The image forming apparatus according to claim 5, wherein the charging unit is a contact type charging unit that applies a DC voltage.   The image forming apparatus according to claim 5, wherein the transfer unit employs a direct transfer method.

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