JP6500840B2 - Electrophotographic photoreceptor - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member.

  The electrophotographic photosensitive member is used in an electrophotographic image forming apparatus. The electrophotographic photosensitive member comprises a photosensitive layer. Examples of the electrophotographic photosensitive member include a laminated type electrophotographic photosensitive member. The multi-layered electrophotographic photosensitive member includes, as a photosensitive layer, a charge generation layer having a charge generation function and a charge transport layer having a charge transport function.

  The photosensitive layer provided in the electrophotographic photosensitive member described in Patent Document 1 contains, for example, a compound represented by the following chemical formula (HT-A) or (HT-B).

Unexamined-Japanese-Patent No. 2012-27139

  However, in the electrophotographic photosensitive member disclosed in Patent Document 1, the electrical characteristics are not sufficient.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an electrophotographic photosensitive member having both electrical characteristics and wear resistance.

  The electrophotographic photosensitive member of the present invention comprises a conductive substrate and a photosensitive layer. The photosensitive layer includes a charge generation layer and a charge transport layer. The charge generating layer contains a charge generating agent. The charge transport layer contains a hole transport agent and a binder resin. The hole transfer agent includes a triarylamine hydrazone derivative represented by the following general formula (1) or (2). The said binder resin contains polycarbonate resin represented by following General formula (3).

In the general formula (1), R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon which may have a substituent It represents an alkoxy group having 1 to 6 atoms, or an aryl group having 6 to 14 carbon atoms which may have a substituent. n and k each independently represent an integer of 1 or more and 3 or less. u and m each independently represent an integer of 0 or more and 5 or less. When k represents 1, R ¹ bonded to different phenyl groups may be identical to or different from ^one another. R ² bonded to different phenyl groups may be identical to or different from one another. When u represents an integer of 2 or more, plural R ¹ bonded to the same phenyl group may be the same as or different from each other. When m represents an integer of 2 or more, plural R ² bonded to the same phenyl group may be the same as or different from each other.

In the general formula (2), each of R ³ and R ⁴ independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon which may have a substituent It represents an alkoxy group having 1 to 6 atoms, or an aryl group having 6 to 14 carbon atoms which may have a substituent. p and q each independently represent an integer of 0 or more and 5 or less. R ³ bonded to different phenyl groups may be identical to or different from one another. R ⁴ bonded to different phenyl groups may be identical to or different from one another. When p represents an integer of 2 or more, plural R ³ bonded to the same phenyl group may be the same as or different from each other. When q represents an integer of 2 or more, plural R ⁴ bonded to the same phenyl group may be the same or different.

In the general formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl having 6 to 14 carbon atoms. Represents a group. R ⁷ and R ⁸ may represent a cycloalkylidene group having 3 to 8 carbon atoms which is formed by bonding to each other.

  According to the electrophotographic photosensitive member of the present invention, both the electrical characteristics and the abrasion resistance can be achieved.

(A), (b) and (c) are each schematic sectional drawing which shows the electrophotographic photoreceptor which concerns on embodiment of this invention. It is a < ¹ > H-NMR spectrum of the triarylamine hydrazone derivative represented by chemical formula (HT-4).

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

  Hereinafter, “system” may be added after the compound name to generically generically refer to the compound and its derivative. Moreover, when a "system" is attached after a compound name and it represents a polymer name, it means that the repeating unit of a polymer originates in a compound or its derivative (s).

  Hereinafter, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon An alkoxy group having 1 to 3 atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylidene group having 3 to 8 carbon atoms, 5 or more carbon atoms The cycloalkylidene group having 7 or less and the heterocyclic group have the following meanings unless otherwise specified.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

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

  The alkyl group having 1 or more and 4 or less carbon atoms is linear or branched and unsubstituted. As a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, or t-butyl group is mentioned, for example.

  The alkyl group having 1 to 3 carbon atoms is linear or branched and unsubstituted. As a C1-C3 alkyl group, a methyl group, an ethyl group, n-propyl group, or isopropyl group is mentioned, for example.

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

  The alkoxy group having 1 to 3 carbon atoms is linear or branched and unsubstituted. As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, or an isopropoxy group is mentioned, for example.

  The aryl group having 6 or more and 14 or less carbon atoms is, for example, an unsubstituted aromatic monocyclic hydrocarbon group having 6 or more and 14 or less carbon atoms, and an unsubstituted aromatic fused bicyclic ring having 6 or more and 14 or less carbon atoms. It is a hydrogen group or a non-substituted aromatic fused tricyclic hydrocarbon group having 6 to 14 carbon atoms. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

  The cycloalkyl group having 3 to 10 carbon atoms is unsubstituted. As a C3-C10 cycloalkyl group, a cyclopropyl group, cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, or a cyclodecyl group is mentioned, for example.

  The cycloalkylidene group having 3 to 8 carbon atoms is unsubstituted. Examples of the cycloalkylidene group having 3 to 8 carbon atoms include cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cyclohexylidene group, cycloheptylidene group, and cyclooctylidene group.

  The cycloalkylidene group having 5 to 7 carbon atoms is unsubstituted. Examples of the cycloalkylidene group having 5 to 7 carbon atoms include a cyclopentylidene group, a cyclohexylidene group, or a cycloheptylidene group.

  Heterocyclic groups are unsubstituted. The heterocyclic group is, for example, a 5- or 6-membered monocyclic heterocyclic group containing one or more (preferably 1 or more and 3 or less) hetero atoms and having aromaticity; such single rings Or a heterocyclic group in which such a single ring and a 5- or 6-membered hydrocarbon ring are fused. The hetero atom is one or more selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom. Specific examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, isothiazolyl group, isoxazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, furazanyl group, pyranyl group, pyridyl group , Pyridazinyl group, pyrimidinyl group, pyrazinyl group, indolyl group, 1H-indazolyl group, isoindolyl group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, pteridinyl group, triazolyl group, tetrazolyl group, 4H-quinolizinyl group, naphthyridinyl group Benzofuranyl group, 1,3-benzodioxolyl group, benzoxazolyl group, benzothiazolyl group or benzimidazolyl group can be mentioned.

<1. Photosensitive body>
An electrophotographic photosensitive member (hereinafter sometimes referred to as a photosensitive member) according to an embodiment of the present invention comprises a conductive substrate and a photosensitive layer. The photosensitive layer includes a charge generation layer and a charge transport layer. The charge generating layer contains a charge generating agent. The charge transport layer contains a hole transport agent and a binder resin. The hole transport agent includes a triarylamine hydrazone derivative represented by the general formula (1) or (2) (hereinafter, each may be described as a triarylamine hydrazone derivative (1) and (2)). A binder resin contains polycarbonate resin (Hereinafter, it may describe as polycarbonate resin (3).) Represented by General formula (3). The photoreceptor according to the present embodiment can have both electrical characteristics and wear resistance. The reason is presumed as follows.

  The triarylamine hydrazone derivatives (1) and (2) have a hydrazone moiety via a phenylethenyl moiety in at least one of the three phenyl groups of the triphenylamine moiety. Since the triarylamine hydrazone derivatives (1) and (2) have such a structure, the spatial spread of the π conjugated system is relatively large, and the triarylamine hydrazone derivative (1) and ((hole) of the carrier (hole) The moving distance within the molecule of 2) tends to be large. That is, the intramolecular migration distance of carriers (holes) tends to be large. In addition, since triarylamine hydrazone derivatives (1) and (2) have a relatively large π spread system in spatial extent, the π of the plurality of triarylamine hydrazone derivatives (1) and (2) in the photosensitive layer is The conjugated systems tend to overlap with each other, and the movement distance between the molecules of the triarylamine hydrazone derivatives (1) and (2) of the carrier (hole) tends to be small. That is, the intermolecular migration distance of carriers (holes) tends to be small. Therefore, it is considered that the acceptability and the transportability of the carrier (hole) are improved, and the electrical property (for example, the sensitivity property) of the photoreceptor is improved.

  Also, since the triarylamine hydrazone derivatives (1) and (2) thus extend the π conjugated system via the phenylethenyl moiety, they are chemically more than the π-conjugated system of the carbon-carbon double bond. It is stable. Moreover, since the triarylamine hydrazone derivatives (1) and (2) have polar hydrazone moieties as described above, they have excellent dispersibility in the photosensitive layer. In addition, the triarylamine hydrazone derivatives (1) and (2) tend to be excellent in compatibility with the polycarbonate resin (3). Thus, the triarylamine hydrazone derivatives (1) and (2) are easily dispersed uniformly in the photosensitive layer.

  Furthermore, since the triarylamine hydrazone derivatives (1) and (2) tend to be excellent in compatibility with the polycarbonate resin (3), it is easy to form a charge transport layer having a high layer density. Therefore, it is considered that the abrasion resistance of the photosensitive member is excellent. Therefore, it is considered that the photoreceptor according to the present embodiment can achieve both the electrical characteristics (for example, the sensitivity characteristics) and the abrasion resistance.

  Hereinafter, the photosensitive member according to the present embodiment will be described in detail. The structure of the photosensitive member 1 will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a photosensitive member which is an example of the photosensitive member 1 according to the present embodiment.

  As shown in FIG. 1A, the photosensitive member 1 includes a conductive substrate 2 and a photosensitive layer 3. Photosensitive layer 3 includes charge generation layer 3a and charge transport layer 3b. In the photosensitive member 1, the charge generation layer 3 a is provided on the conductive substrate 2, and the charge transport layer 3 b is provided on the charge generation layer 3 a.

  As shown in FIG. 1B, in the photosensitive member 1, the charge transport layer 3b may be provided on the conductive substrate 2, and the charge generation layer 3a may be provided on the charge transport layer 3b.

  As shown in FIG. 1C, the photosensitive member 1 may be provided with a conductive substrate 2, a photosensitive layer 3 and an intermediate layer (undercoat layer) 4. The intermediate layer 4 is provided between the conductive substrate 2 and the photosensitive layer 3. In addition, a protective layer may be provided on the photosensitive layer 3.

  The thicknesses of the charge generation layer 3a and the charge transport layer 3b are not particularly limited as long as the functions as the respective layers can be sufficiently exhibited. The thickness of the charge generation layer 3a is preferably 0.01 μm or more and 5 μm or less, and more preferably 0.1 μm or more and 3 μm or less. The thickness of the charge transport layer 3 b is preferably 2 μm or more and 100 μm or less, and more preferably 5 μm or more and 50 μm or less.

  The charge generation layer 3a of the photosensitive layer 3 may contain a binder resin for charge generation layer (hereinafter sometimes referred to as a base resin). The charge generation layer 3a and the charge transport layer 3b may contain various additives, as necessary. Hereinafter, each component of the photoreceptor (conductive substrate, charge generating agent, hole transporting agent, binder resin, base resin, additive, and intermediate layer) will be described. Furthermore, a method of manufacturing the photosensitive member will be described.

<2. Conductive substrate>
The conductive substrate is not particularly limited as long as it can be used as the conductive substrate of the photoreceptor. The conductive substrate may be formed at least at a surface portion of a material having conductivity. Examples of the conductive substrate include a conductive substrate formed of a material having conductivity, or a conductive substrate coated with a material having conductivity. As a material which has electroconductivity, aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, or a brass is mentioned, for example. These materials having conductivity may be used alone or in combination of two or more. As a combination of two or more, for example, an alloy may be mentioned. Among these materials having conductivity, aluminum or an aluminum alloy is preferable because charge transfer from the photosensitive layer to the conductive substrate is good.

  The shape of the conductive substrate is appropriately selected in accordance with the structure of the image forming apparatus. Examples of the shape of the conductive substrate include a sheet or a drum. In addition, the thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.

<3. Charge generator>
The charge generating agent is not particularly limited as long as it is a charge generating agent for a photoreceptor. Examples of charge generating agents include phthalocyanine pigments, perylene pigments, bisazo pigments, trisazo pigments, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squalene pigments, indigo pigments, azulenium pigments, cyanines Powder, powder of inorganic photoconductive material (more specifically, selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide or amorphous silicon etc.), pyrylium pigment, anthanthrone pigment, triphenylmethane pigment, slen type And pigments such as toluidine pigments, pyrazoline pigments, and quinacridone pigments. The charge generating agent may be used alone or in combination of two or more.

  As a phthalocyanine-type pigment, the metal free phthalocyanine (it may describe as a compound (C-1) hereafter) or metal phthalocyanine represented by Chemical formula (C-1) is mentioned, for example. As a metal phthalocyanine, the titanyl phthalocyanine (Hereinafter, it may describe as a compound (C-2), respectively.) Represented by Chemical formula (C-2), a hydroxygallium phthalocyanine, or a chlorogallium phthalocyanine is mentioned. The phthalocyanine pigment may be crystalline or non-crystalline. The crystal form (for example, α-type, β-type, Y-type, V-type, or II-type) of the phthalocyanine-based pigment is not particularly limited, and phthalocyanine-based pigments having various crystal forms are used.

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

  For example, in a digital optical image forming apparatus (for example, a laser beam printer or a facsimile using a light source such as a semiconductor laser), it is preferable to use a photosensitive member having sensitivity in a wavelength region of 700 nm or more. As a charge generating agent, phthalocyanine pigments are preferable, metal-free phthalocyanines or titanyl phthalocyanines are more preferable, and X-type metal-free phthalocyanines or Y-type titanyl phthalocyanines are more preferable because they have high quantum yield in a wavelength region of 700 nm or more. . In the case where the charge transport layer contains the triarylamine hydrazone derivative (1) or (2), in order to particularly improve the electrical properties of the photoreceptor, Y-type titanyl phthalocyanine as a charge generation agent is more preferable.

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

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

  When the photoreceptor is applied to an image forming apparatus using a short wavelength laser light source, an anthanthrone pigment is suitably used as a charge generating agent. The wavelength of the short wavelength laser light is, for example, 350 nm or more and 550 nm or less.

  The content of the charge generating agent is preferably 5 parts by mass or more and 1000 parts by mass or less, and 30 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the base resin contained in the charge generation layer. More preferable.

<4. Hole transport agent>
[4-1. Triarylamine Hydrazone Derivative]
Hole transport agents include triarylamine hydrazone derivatives (1) or (2). The triarylamine hydrazone derivatives (1) and (2) are represented by the general formulas (1) and (2), respectively.

In the general formula (1), R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom which may have a substituent This represents an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent. n and k each independently represent an integer of 1 or more and 3 or less. u and m each independently represent an integer of 0 or more and 5 or less. When k represents 1, R ¹ bonded to different phenyl groups may be identical to or different from ^one another. R ² bonded to different phenyl groups may be identical to or different from one another. When u represents an integer of 2 or more, plural R ¹ bonded to the same phenyl group may be the same as or different from each other. When m represents an integer of 2 or more, plural R ² bonded to the same phenyl group may be the same as or different from each other.

In General Formula (2), R ³ and R ⁴ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a carbon atom which may have a substituent This represents an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms which may have a substituent. p and q each independently represent an integer of 0 or more and 5 or less. R ³ bonded to different phenyl groups may be identical to or different from one another. R ⁴ bonded to different phenyl groups may be identical to or different from one another. When p represents an integer of 2 or more, plural R ³ bonded to the same phenyl group may be the same as or different from each other. When q represents an integer of 2 or more, plural R ⁴ bonded to the same phenyl group may be the same or different.

In the general formula (1), the alkyl group having 1 to 6 carbon atoms represented by R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² may have a substituent. As such a substituent, for example, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a heterocyclic ring Groups are mentioned.

In the general formula (1), the alkoxy group having 1 to 6 carbon atoms represented by R ¹ and R ² may have a substituent. As such a substituent, for example, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a heterocyclic ring Groups are mentioned.

In the general formula (1), the aryl group having 6 to 14 carbon atoms represented by R ¹ and R ² may have a substituent. As such a substituent, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, 3 carbon atoms More than 10 or less cycloalkyl groups or heterocyclic groups may be mentioned.

The substitution position of R ¹ includes the ortho position (o position), meta position (m position) or para position (p position) of the phenyl group with respect to the bonding position to the alkenyl group, and the para position is preferable. The substitution position of R ² includes the ortho, meta or para position of the phenyl group with respect to the bonding position to the nitrogen atom.

In General Formula (1), R ¹ represents an alkyl group having 1 to 3 carbon atoms, u preferably represents 0 or 1, and m preferably represents 0.

  In the general formula (1), n preferably represents a relatively large number, and more preferably 2 or 3 in order to further improve the electrical properties of the photoreceptor. Since the number represented by n means the number of carbon-carbon double bonds, as n increases, the spatial extension of the π conjugated system of the triarylamine hydrazone derivative (1) increases, and the intramolecular molecule of the carrier (hole) It is considered that the increase in the migration distance and the reduction in the intermolecular migration distance further improve the acceptability and transportability of the carrier (hole).

  In the general formula (1), n preferably represents a relatively small number, and more preferably 1 to further improve the abrasion resistance of the photoreceptor.

  In the general formula (1), k preferably represents a relatively small number, and more preferably 1 to further improve the abrasion resistance of the photosensitive member.

In the general formula (2), the alkyl group having 1 to 6 carbon atoms represented by R ³ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. The alkyl group having 1 to 6 carbon atoms represented by R ³ and R ⁴ may have a substituent. As such a substituent, for example, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a heterocyclic ring Groups are mentioned.

In general formula (2), the alkoxy group having 1 to 6 carbon atoms represented by R ³ and R ⁴ may have a substituent. As such a substituent, for example, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or a heterocyclic ring Groups are mentioned.

In the general formula (2), the aryl group having 6 to 14 carbon atoms represented by R ³ and R ⁴ may have a substituent. As such a substituent, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, 3 carbon atoms More than 10 or less cycloalkyl groups or heterocyclic groups may be mentioned.

The substitution position of R ³ and R ⁴ includes the ortho position, meta position or para position of the phenyl group with respect to the bonding position to the nitrogen atom. The substitution position of R ³ is preferably para.

In general formula (2), R ³ preferably represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, p represents 1 and q preferably represents 0.

  Specific examples of the triarylamine hydrazone derivative (1) include triarylamine hydrazone derivatives represented by the chemical formulas (HT-1) to (HT-3) and (HT-5) to (HT-7) (hereinafter referred to as And triarylamine hydrazone derivatives (HT-1) to (HT-3) and (HT-5) to (HT-7), respectively. Specific examples of the triarylamine hydrazone derivative (2) include a triarylamine hydrazone derivative represented by a chemical formula (HT-4) (hereinafter sometimes referred to as a triarylamine hydrazone derivative (HT-4)). It can be mentioned.

  Among these triarylamine hydrazone derivatives (HT-1) to (HT-7), triarylamine hydrazone derivatives (HT-4) and (HT-6) are preferable from the viewpoint of cost.

[4-2. Production of Triarylamine Hydrazone Derivative]
[4-2-1. Synthesis of triarylamine hydrazone derivative (1)]
The triarylamine hydrazone derivative (1) is described, for example, as reaction formulas (R-1) to (R-6) represented by reaction formulas (R-1) to (R-6) (hereinafter referred to as reactions (R-1) to (R-6), respectively. May be manufactured by the method according to or similar to this. In the reactions (R-1) to (R-2), a diphenyl alkene derivative represented by the general formula (E) (hereinafter sometimes referred to as a diphenyl alkene derivative (E)) is obtained. In the reactions (R-3) to (R-5), a hydrazone derivative represented by the general formula (L) (hereinafter sometimes referred to as a hydrazone derivative (L)) is obtained. In the reaction (R-6), a triarylamine hydrazone derivative (1) is obtained.

[Reaction (R-1) to (R-2)]
In reaction (R-1) ~ (R -2), R 1 and u are respectively the same as R ¹ and u in the general formula (1). X represents a halogen atom, preferably a chlorine atom. Further, n1 and n2 each independently represent an integer of 0 or more, and n1, n2 and n satisfy the equation n = n1 + n2 + 1.

  In the reaction (R-1), a benzene derivative represented by the general formula (A) (hereinafter sometimes referred to as a benzene derivative (A)) and triethyl phosphite represented by the chemical formula (B) The reaction is carried out to obtain a phosphonate derivative represented by the general formula (C) (hereinafter sometimes referred to as a phosphonate derivative (C)).

  The reaction ratio of benzene derivative (A) to triethyl phosphite [benzene derivative (A): triethyl phosphite] is 1: 1 to 1: 2.5 in mass ratio (molar ratio) preferable. If the substance mass of triethyl phosphite is 1 mol or more with respect to 1 mol of the substance mass of the benzene derivative (A), the yield of the phosphonate derivative (C) hardly decreases. On the other hand, when the substance mass of triethyl phosphite is 2.5 mol or less with respect to 1 mol of substance of benzene derivative (A), unreacted triethyl phosphite remains after reaction (R-1). The phosphonate derivative (C) is easy to purify. The reaction temperature in the reaction (R-1) is preferably 160 ° C. or more and 200 ° C. or less, and the reaction time is preferably 2 hours or more and 10 hours or less.

  In the reaction (R-2), the phosphonate derivative (C) is reacted with an aldehyde derivative represented by the general formula (D) (hereinafter sometimes referred to as an aldehyde derivative (D)) to obtain a diphenyl alkene derivative Get (E). The reaction (R-2) is a Wittig reaction.

  The reaction ratio of the phosphonate derivative (C) to the aldehyde derivative (D) [phosphonate derivative (C): aldehyde derivative (D)] is preferably 1: 1 to 1: 2.5 in molar ratio. If the substance mass of the aldehyde derivative (D) is 1 mol or more relative to 1 mol of the substance mass of the phosphonate derivative (C), the yield of the diphenyl alkene derivative (E) does not easily decrease. Unreacted aldehyde derivative (D) hardly remains when the substance amount of aldehyde derivative (D) is 2.5 mol or less with respect to 1 mol of substance amount of phosphonate derivative (C), diphenyl alkene derivative (E) Purification of

  The reaction (R-2) can be carried out in the presence of a base. As a base to be used, for example, sodium alkoxide (more specifically, sodium methoxide or sodium ethoxide etc.), metal hydride (more specifically, sodium hydride or potassium hydride etc.), or Metal salts (more specifically, n-butyllithium and the like) can be mentioned. One of these bases may be used alone, or two or more of these bases may be used in combination.

  It is preferable that the addition amount of a base is 1 mol or more and 2 mol or less with respect to 1 mol of substance mass of aldehyde derivative (D). If the addition amount of the base is 1 mol or more with respect to 1 mol of the substance mass of the aldehyde derivative (D), the reactivity is unlikely to be lowered. On the other hand, when the addition amount of the base is 2 mol or less with respect to 1 mol of substance mass of the aldehyde derivative (D), control of the reaction becomes easy.

  The reaction (R-2) can be carried out in a solvent. As the solvent, for example, ethers (more specifically, tetrahydrofuran, diethyl ether or dioxane etc.), halogenated hydrocarbons (more specifically, methylene chloride, chloroform or dichloroethane etc.), or aromatic carbonized Hydrogen (more specifically, benzene, toluene or the like) can be mentioned.

  In the reaction (R-2), the reaction temperature is preferably 0 ° C. or more and 50 ° C. or less, and the reaction time is preferably 2 hours or more and 24 hours or less.

[Reaction (R-1 ')-(R-2')]
In addition, the diphenyl alkene derivative (E) is a reaction represented by a reaction formula (R-1 ') to (R-2') (hereinafter referred to as a reaction (R-1 ') to (R-2'), respectively) It can also be obtained by In reaction (R-1 ') ~ ( R-2'), R 1 and u are respectively the same as R ¹ and u in the general formula (1). X represents a halogen atom, preferably a chlorine atom. Further, n3 and n4 each independently represent an integer of 0 or more, and n3, n4 and n satisfy the equation n = n3 + n4 + 1.

In the reactions (R-1 ′) to (R-2 ′), a phosphonate derivative is synthesized from a reactant (Reactant) having a substituent R ¹ in comparison with the reactions (R-1) to (R-2), It differs in the point which synthesize | combines a diphenyl alkene derivative (E) finally. Specifically, the reaction (R-1 ′) is the same as the benzene derivative (A) except that it is changed to the benzene derivative represented by the general formula (A ′) (hereinafter, the benzene derivative (A ′) may be described) , The same reaction as the reaction (R-1). In addition, in the reaction (R-2 ′), the phosphonate derivative (C) and the aldehyde derivative (D) may each be described as a phosphonate derivative represented by the general formula (C ′) (hereinafter referred to as a phosphonate derivative (C ′) The reaction is the same as the reaction (R-2) except that the aldehyde derivative represented by the general formula (D ′) is changed to an aldehyde derivative (hereinafter sometimes referred to as an aldehyde derivative (D ′)).

[Reaction (R-3) to (R-5)]
In reaction (R-3) ~ (R -5), R 2 and m are respectively the same as R ² and m in the general formula (1). X represents a halogen atom, preferably a chlorine atom.

  In the reaction (R-3), a benzene derivative represented by the general formula (F) (hereinafter sometimes referred to as a benzene derivative (F)) and triethyl phosphite represented by the chemical formula (B) The reaction is carried out to obtain a phosphonate derivative represented by the general formula (G) (hereinafter sometimes referred to as a phosphonate derivative (G)).

  The reaction ratio of the benzene derivative (F) to triethyl phosphite [benzene derivative (F): triethyl phosphite] is preferably 1: 1 to 1: 2.5 in molar ratio. If the substance mass of triethyl phosphite is 1 mol or more with respect to 1 mol of substance mass of the benzene derivative (F), the yield of the phosphonate derivative (G) hardly decreases. On the other hand, when the substance mass of triethyl phosphite is 2.5 mol or less with respect to 1 mol of substance of benzene derivative (F), unreacted triethyl phosphite remains after the reaction (R-3). It is difficult to purify the phosphonate derivative (G). In the reaction (R-3), the reaction temperature is preferably 160 ° C. or more and 200 ° C. or less, and the reaction time is preferably 2 hours or more and 10 hours or less.

  In the reaction formula (R-4), a phosphonate derivative (G) and a terephthalaldehyde represented by the chemical formula (H) are reacted to form a diphenyl ethene derivative represented by the general formula (J) (hereinafter, a diphenyl ethene derivative To obtain (J)). The reaction (R-4) is a Wittig reaction.

  The reaction ratio of phosphonate derivative (G) to terephthalaldehyde [phosphonate derivative (G): terephthalaldehyde] is preferably 1: 1 to 1: 2.5 in molar ratio. If the substance mass of terephthalaldehyde is 1 mol or more with respect to 1 mol of the substance mass of the phosphonate derivative (G), the yield of the diphenyl ethene derivative (J) hardly decreases. When the substance amount of terephthalaldehyde is 2.5 moles or less with respect to 1 mol of the substance of phosphonate derivative (G), unreacted terephthalaldehyde is difficult to remain, and purification of diphenyl ethene derivative (J) becomes easy. .

  The reaction (R-4) can be carried out in the presence of a base. As a base to be used, the base illustrated by reaction (R-2) is mentioned, for example. One type of base may be used alone, or two or more types may be used in combination.

  The amount of the base added is preferably 1 or more and 2 or less per 1 mol of terephthalaldehyde. If the addition amount of the base is 1 mol or more with respect to 1 mol of the substance mass of terephthalaldehyde, the reactivity is unlikely to be lowered. On the other hand, when the addition amount of the base is 2 mol or less with respect to 1 mol of substance mass of terephthalaldehyde, control of the reaction becomes easy.

  The reaction (R-4) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction (R-2) is mentioned, for example.

  In the reaction (R-4), the reaction temperature is preferably 0 ° C. or more and 50 ° C. or less, and the reaction time is preferably 2 hours or more and 24 hours or less.

  In the reaction (R-5), the aldehyde is a diphenyl ethene derivative (J) which is an aldehyde, and an amine derivative which is a primary amine and is represented by a chemical formula (K) (hereinafter sometimes referred to as an amine derivative (K)) The hydrazone derivative (L) is obtained by condensation reaction with (primary amine) in the presence of a catalyst and oxidation. The amine derivative (K) may be added in the form of a salt (eg, hydrochloride). The reaction ratio of diphenylethene derivative (J) to amine derivative (K) [diphenylethene derivative (J): amine derivative (K)] is preferably 1: 1 to 1: 2.5 in molar ratio. If the substance mass of the amine derivative (K) is 1 mol or more with respect to 1 mol of the substance mass of the diphenyl ethene derivative (J), the yield of the hydrazone derivative (L) does not easily decrease. When the substance mass of the amine derivative (K) is 2.5 mol or less with respect to 1 mol of the substance mass of the diphenyl ethene derivative (J), the unreacted amine derivative (K) hardly remains, and the hydrazone derivative (L) Purification of In the reaction (R-5), 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. The reaction (R-5) can be carried out in a solvent. Examples of the solvent include toluene, xylene, methanol, ethanol, tetrahydrofuran or N, N-dimethylformamide. The reaction (R-5) can be carried out in the presence of an acid catalyst. As an acid catalyst, p-toluenesulfonic acid, concentrated sulfuric acid, or hydrochloric acid is mentioned, for example.

[Reaction (R-6)]
In reaction ^{(R-6), R 1} , R 2, u, m, n, and k is a ^{R 1, R 2, u,} m, n, and k as defined respectively in formula (1) . X represents a halogen atom, preferably a chlorine atom.

  Reaction (R-6) may be described, for example, as reactions represented by reaction formulas (R-7) to (R-8) (hereinafter, referred to as reactions (R-7) to (R-8), respectively. Or a reaction represented by a reaction formula (R-7 ′) to (R-8 ′) (hereinafter, each may be described as a reaction (R-7 ′) to (R-8 ′)), The triarylamine hydrazone derivative (1) is obtained.

In reactions (R-7) to (R-8), first, LiNH ₂ (lithium amide) is reacted with a diphenyl alkene derivative (E) to form an intermediate amine derivative (M), and then a hydrazone The derivative (L) is reacted with the obtained amine derivative (M) to form a triarylamine hydrazone derivative (1). In reaction (R-7) ~ (R -8), R 1, R 2, u, m, and ^{n, R 1, R 2, u} , m, and n as defined respectively in formula (1) It is. X represents a halogen atom, preferably a chlorine atom.

In the reaction formula (R-7), for example, an amine derivative which is an intermediate product by reacting (3-k) molar equivalents of diphenyl alkene derivative (E) with 1 molar equivalent of lithium amide (LiNH ₂ ) (M) (not described in reaction formulas (R-7) to (R-8)) is obtained. The reaction (R-7) is a coupling reaction. Said k is synonymous with k in General formula (1). When k represents 3, it passes through only reaction (R-8) mentioned later, without going through reaction (R-7). In such a case, triarylamine hydrazone derivative (1) is obtained in the same manner as in reaction (R-8) except that amine derivative (M) is changed to lithium amide. For example, when synthesizing a triarylamine hydrazone derivative (HT-7).

  The reaction ratio of the diphenyl alkene derivative (E) to the lithium amide [diphenyl alkene derivative (E): lithium amide] is preferably 5: 1 to 1: 1 in molar ratio. If the substance mass of the diphenyl alkene derivative (E) is 1 mol or more with respect to 1 mol of substance mass of lithium amide, the yield of the amine derivative (M) hardly decreases. On the other hand, when the substance mass of the diphenyl alkene derivative (E) is 5 mol or less with respect to 1 mol of substance mass of lithium amide, unreacted diphenyl alkene derivative (E) remains after the reaction (R-7). And the purification of the amine derivative (M) is facilitated.

  In the reaction (R-7), 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.

  In the reaction (R-7), it is preferable to use a palladium compound as a catalyst. Thereby, the activation energy in reaction formula (R-7) can be reduced. As a result, the yield of the amine derivative (M) can be further improved.

  As a palladium compound, a tetravalent palladium compound, a bivalent palladium compound, or other palladium compounds are mentioned, for example. Examples of tetravalent palladium compounds include sodium hexachloropalladium (IV) tetrahydrate or potassium hexachloropalladium (IV) tetrahydrate. Examples of divalent palladium compounds include palladium (II) chloride, palladium (II) bromide, palladium (II) acetate, palladium acetyl acetate (II), dichlorobis (benzonitrile) palladium (II), and dichlorbis (triphenyl). Phosphine) palladium (II), dichlorotetraminepalladium (II), or dichloro (cycloocta-1,5-diene) palladium (II). Other palladium compounds include, for example, tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), or tetrakis (triphenylphosphine) palladium (0) . Moreover, a palladium compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of addition of the palladium compound is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1 mol or less with respect to 1 mol of the substance mass of the diphenyl alkene derivative (E). .

  The palladium compound may have a structure containing a ligand. Thereby, the reactivity of reaction (R-7) can be improved. As a ligand, for example, tricyclohexyl phosphine, triphenyl phosphine, methyl diphenyl phosphine, triflyl phosphine, tri (o-tolyl) phosphine, dicyclohexyl phenyl phosphine, tri (t-butyl) phosphine, 2,2'-bis (Diphenylphosphino) -1,1′-binaphthyl or 2,2′-bis [(diphenylphosphino) diphenyl] ether. One type of ligand may be used alone, or two or more types may be used in combination. The addition amount of the ligand 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 substance mass of the diphenyl alkene derivative (E). preferable.

  The reaction (R-7) is preferably carried out in the presence of a base. As a result, hydrogen halide generated in the reaction system is rapidly neutralized, and catalyst activity can be improved. As a result, the yield of the amine derivative (M) can be improved.

  The base may be an inorganic base or an organic base. As the organic base, for example, alkali metal alkoside (more specifically, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, etc.) Is preferred, and sodium methoxide is more preferred. As an inorganic base, a tripotassium phosphate or cesium fluoride is mentioned, for example.

  The reaction (R-7) can be carried out in a solvent. As the solvent, for example, xylene, toluene, tetrahydrofuran or dimethylformamide can be mentioned.

  In the reaction (R-8), for example, k molar equivalents of the hydrazone derivative (L) and the one molar equivalent of the amine derivative (M) obtained in the reaction (R-7) are reacted to obtain a triarylamine hydrazone The derivative (1) is obtained. The reaction (R-8) is a coupling reaction. Said k is synonymous with k in General formula (1).

  The reaction ratio of the hydrazone derivative (L) to the amine derivative (M) [hydrazone derivative (L): intermediate compound] is preferably 5: 1 to 1: 1 in molar ratio. The yield of triarylamine hydrazone derivative (1) does not fall easily that the amount of hydrazone derivative (L) substance is 1 mol or more with respect to 1 mol of substance weights of amine derivative (M). On the other hand, when the hydrazone derivative (L) substance mass is 5 moles or less per 1 mol of amine derivative (M) substance mass, unreacted hydrazone derivative (L) hardly remains after the reaction (R-8) The triarylamine hydrazone derivative (1) is easily purified.

  In the reaction (R-8), 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.

  In the reaction (R-8), it is preferable to use a palladium compound as a catalyst. Thereby, the activation energy in the reaction (R-8) can be reduced. As a result, the yield of the triarylamine hydrazone derivative (1) can be further improved.

  As a palladium compound, the palladium compound illustrated by reaction (R-7) is mentioned, for example. The palladium compound may be used alone or in combination of two or more.

  The amount of addition of the palladium compound is preferably 0.0005 mol or more and 20 mol or less, and more preferably 0.001 mol or more and 1 mol or less, per 1 mol of substance mass of the hydrazone derivative (L).

  Such palladium catalyst may have a structure containing a ligand. Thereby, the reactivity of reaction (R-8) can be improved. As a ligand, the ligand illustrated by reaction (R-7) is mentioned, for example. One type of ligand may be used alone, or two or more types may be used in combination. 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 substance mass of hydrazone derivative (L). .

  The reaction (R-8) is preferably carried out in the presence of a base. As a result, hydrogen halide generated in the reaction system is rapidly neutralized, and catalyst activity can be improved. As a result, the yield of the triarylamine hydrazone derivative (1) can be improved.

  The base may be an inorganic base or an organic base. As an organic base and an inorganic base, the organic base and the inorganic base which are illustrated by reaction formula (R-7) are mentioned, for example.

  When 0.0005 mol or more and 20 mol or less of palladium compound is added to 1 mol of substance mass of hydrazone derivative (L), the addition amount of the base is preferably 1 mol or more and 10 mol or less, and 1 mol or more More preferably, it is 5 moles or less.

  The reaction (R-8) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction represented by reaction formula (R-7) is mentioned, for example.

[Reaction (R-7 ') to (R-8')]
In reactions (R-7 ') to (R-8'), for example, 1 molar equivalent of LiNH ₂ is reacted with k molar equivalents of hydrazone derivative (L) to form an intermediate amine derivative (N) And then reacting the diphenyl alkene derivative (E) with the obtained amine derivative (N) (not described in the reaction formulas (R-7 ') to (R-8')) to obtain a triarylamine hydrazone derivative Generate (1). In reaction (R-7 ') ~ ( R-8'), R 1, R 2, u, m, and n, R ^1, respectively in the general formula ^{(1), R 2, u} , m, and n It is synonymous with X represents a halogen atom, preferably a chlorine atom. Said k is synonymous with k in General formula (1).

The reaction (R-7 ′) is the same reaction as the reaction (R-7) except that the diphenyl alkene derivative (E) is changed to the hydrazone derivative (L) and the reaction ratio is changed. The reaction (R-8 ′) is an amine derivative (N) formed by the reaction of hydrazone derivative (L) and LiNH ₂ with the amine derivative (M) formed by the reaction of diphenyl alkene derivative (E) and LiNH ₂ The reaction is the same as the reaction (R-8) except that the reaction ratio is changed, and the hydrazone derivative (L) is changed to the diphenyl alkene derivative (E).

When the triarylamine hydrazone derivative (1) in which k represents 3 is synthesized (for example, when the triarylamine hydrazone derivative (HT-7) is synthesized), the reaction substance (R-7 ′) is a reactant (R-7 ′). The ratio of the amount of substance of Reactant (LiNH ₂ : hydrazone derivative (L)) can be synthesized, for example, as 1: 3. In such a case, triarylamine hydrazone derivative (1) in which k represents 3 is obtained without undergoing reaction (R-8 ′).

  In addition to these reactions, appropriate steps (for example, purification steps) may be included as needed. As a purification method, for example, a known method (more specifically, filtration, chromatography, crystallization, etc.) can be mentioned.

4-2-2. Synthesis of triarylamine hydrazone derivative (2)]
The triarylamine hydrazone derivative (2) is produced, for example, according to the reaction represented by the reaction formula (R-9) (hereinafter sometimes referred to as reaction (R-9)) or a method analogous thereto .

In reaction ^{(R-9), R 3} , R 4, p, and q are R ³ respectively in general formula ^{(2), R 4, p} , and the q synonymous. X represents a halogen atom, preferably a chlorine atom.

  In the reaction (R-9), for example, one molar equivalent of the hydrazone derivative represented by the chemical formula (P) (hereinafter sometimes referred to as the hydrazone derivative (P)) and one molar equivalent of the chemical formula (Q) A triarylamine hydrazone derivative (2) is synthesized by reacting it with a diphenylamine derivative (hereinafter sometimes referred to as a diphenylamine derivative (Q)).

  The reaction ratio between the hydrazone derivative (P) and the diphenylamine derivative (Q) [hydrazone derivative (P): diphenylamine derivative (Q)] is preferably 5: 1 to 1: 1 in molar ratio. If the substance mass of the hydrazone derivative (P) is 1 mol or more per 1 mol of the substance mass of the diphenylamine derivative (Q), the yield of the triarylamine hydrazone derivative (2) hardly decreases. On the other hand, when the substance mass of the hydrazone derivative (P) is 5 mol or less per 1 mol of substance mass of the diphenylamine derivative (Q), unreacted hydrazone derivative (P) remains after the reaction (R-9) It is difficult to purify the triarylamine hydrazone derivative (2).

  In the reaction (R-9), 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.

  In the reaction (R-9), it is preferable to use a palladium compound as a catalyst. Thereby, the activation energy in the reaction (R-9) can be reduced. As a result, the yield of the triarylamine hydrazone derivative (2) can be further improved.

  As a palladium compound, the palladium compound illustrated by reaction (R-7) is mentioned, for example. The palladium compound may be used alone or in combination of two or more.

  The amount of addition 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, per 1 mol of substance mass of hydrazone derivative (P).

  Such palladium catalyst may have a structure containing a ligand. Thereby, the reactivity of reaction (R-9) can be improved. As a ligand, the ligand illustrated by reaction (R-7) is mentioned, for example. One type of ligand may be used alone, or two or more types may be used in combination. 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 substance mass of hydrazone derivative (P). .

  The reaction (R-9) is preferably performed in the presence of a base. As a result, hydrogen halide generated in the reaction system is rapidly neutralized, and catalyst activity can be improved. As a result, the yield of the triarylamine hydrazone derivative (2) can be improved.

  The base may be an inorganic base or an organic base. As an organic base and an inorganic base, the organic base and inorganic base which were illustrated by reaction (R-7) are mentioned, for example.

  When 0.0005 mol or more and 20 mol or less of the palladium compound is added to 1 mol of substance mass of hydrazone derivative (P), the addition amount of the base is preferably 1 mol or more and 10 mol or less, and 1 mol More preferably, it is at least 5 moles.

  The reaction (R-9) can be carried out in a solvent. As a solvent, the solvent illustrated by reaction (R-7) is mentioned, for example.

  In addition to these reactions, appropriate steps (for example, purification steps) may be included as necessary. As a purification method, for example, a known method (more specifically, filtration, chromatography, crystallization, etc.) can be mentioned.

[4-3. Other hole transport agent]
The photosensitive layer may contain a hole transport agent other than the triarylamine hydrazone derivatives (1) and (2). As such a hole transport agent, for example, a nitrogen-containing cyclic compound or a fused polycyclic compound can be used. Examples of nitrogen-containing cyclic compounds and condensed polycyclic compounds include diamine derivatives (eg, N, N, N ′, N′-tetraphenylphenylenediamine derivatives, N, N, N ′, N′-tetraphenyl naphthy N, N, N ′, N′-tetraphenylphenanthrylenediamine derivatives), oxadiazole compounds (eg, 2,5-di (4-methylaminophenyl) -1,3,4-) Oxadiazole), styryl compound (eg, 9- (4-diethylaminostyryl) anthracene), carbazole compound (eg, polyvinyl carbazole), organic polysilane compound, pyrazoline compound (eg, 1-phenyl-3- (p-dimethyl) Aminophenyl) pyrazoline), hydrazone compounds, indole compounds, oxazole compounds Isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compound, or triazole-based compounds. One of these hole transport agents may be used alone, or two or more thereof may be used in combination.

  The content of the triarylamine hydrazone derivative (1) or (2) is preferably 80 parts by mass or more and 90 parts by mass or more with respect to 100 parts by mass of the hole transfer agent contained in the photosensitive layer. Is more preferable, and 100 parts by mass is more preferable.

  The content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, and 20 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the charge transport layer. Is more preferred.

<5. Binder resin>
The binder resin comprises a polycarbonate resin (3). The polycarbonate resin (3) has a repeating unit represented by the general formula (3).

In the general formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 14 carbon atoms Represents R ⁷ and R ⁸ may represent a cycloalkylidene group having 3 to 8 carbon atoms which is formed by bonding to each other.

In the general formula (3), the alkyl group having 1 to 4 carbon atoms represented by R ⁵ and R ^6, a methyl group is preferable. As an alkyl group having 1 to 4 carbon atoms represented by R ⁷ and R ⁸ , a methyl group or an ethyl group is preferable.

In the general formula (3), a cycloalkylidene group having 3 to 8 carbon atoms formed by bonding R ⁷ and R ⁸ to each other is more preferably a cycloalkylidene group having 5 to 7 carbon atoms, Den groups are preferred.

In general formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are different from each other Or R ⁷ and R ⁸ preferably represent a cycloalkylidene group having 5 to 7 carbon atoms which is formed by bonding to each other.

In order to further improve the electrical properties of the photoreceptor, in the general formula (3), R ⁷ and R ⁸ each represent an alkyl group having 1 to 4 carbon atoms, or 5 or more carbon atoms formed by bonding to each other It is preferable to represent 7 or less cycloalkylidene group.

In order to further improve the abrasion resistance of the photoreceptor, in the general formula (3), R ⁷ and R ⁸ preferably represent a cycloalkylidene group having 5 to 7 carbon atoms which is formed by bonding to each other .

  Specific examples of the polycarbonate resin (3) include polycarbonate resins having repeating units represented by chemical formulas (Resin-1) to (Resin-4) (hereinafter, polycarbonate resins (Resin-1) to (Resin-4), respectively) May be described).

The method for producing the polycarbonate resin (3) is not particularly limited as long as the polycarbonate resin (3) can be produced. These production methods include, for example, phosgene method, transesterification reaction method, or other known methods. The phosgene method is a method of interfacial condensation polymerization of a diol compound (for example, a diol compound represented by General Formula (3-1)) for forming a repeating unit of a polycarbonate resin (3) and a carbonyl dihalide. The transesterification method is a transesterification reaction of a diol compound and diphenyl carbonate. The interfacial polycondensation reaction may be performed, for example, using a dihalogenated carbonyl (more specifically, phosgene or the like) in the presence of an acid binder and a solvent. In general formula (3-1) R ^5, R ^6, R ⁷ in, and R ⁸ is R ^5, R ^6, R ⁷ respectively in Formula (3), and the R ⁸ synonymous.

  The binder resin may contain another binder resin other than the polycarbonate resin (3). As other binder resin, a thermoplastic resin, a thermosetting resin, or a photocurable resin is mentioned, for example. As a thermoplastic resin, for example, polycarbonate resin (polycarbonate resin other than polycarbonate resin (3)), polyarylate resin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic acid Polymer, styrene-acrylic acid copolymer, polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate copolymer, alkyd resin, Examples thereof include polyamide resins, urethane resins, polysulfone resins, diallyl phthalate resins, ketone resins, polyvinyl butyral resins, polyester resins and polyether resins. As a thermosetting resin, a silicone resin, an epoxy resin, a phenol resin, a urea resin, or a melamine resin is mentioned, for example. Examples of the photocurable resin include epoxy-acrylic acid resins (acrylic acid derivative adducts of epoxy compounds) or urethane-acrylic acid resins (acrylic acid derivative adducts of urethane compounds). One of these binder resins may be used alone, or two or more thereof may be used in combination.

  The viscosity average molecular weight of the binder resin is preferably 40,000 or more, more preferably 40,000 or more and 52,500 or less, and still more preferably 45,000 or more and 50,500 or less. When the viscosity average molecular weight of the binder resin is 40,000 or more, the abrasion resistance of the photosensitive member can be easily improved. When the viscosity average molecular weight of the binder resin is 52,500 or less, the binder resin is easily dissolved in the solvent when the photosensitive layer is formed, and the viscosity of the charge transport layer coating liquid does not become too high. As a result, it becomes easy to form a charge transport layer.

<6. Base resin>
The charge generation layer contains a base resin. The base resin is not particularly limited as long as it is a base resin applicable to the photoreceptor. The base resin may, for example, be a thermoplastic resin, a thermosetting resin or a photocurable resin. As a thermoplastic resin, for example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene-acrylic acid copolymer, acrylic acid polymer, polyethylene resin, ethylene-vinyl acetate Copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide resin, urethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin And ketone resins, polyvinyl butyral resins, polyether resins or polyester resins. As a thermosetting resin, a silicone resin, an epoxy resin, a phenol resin, a urea resin, a melamine resin, or the other thermosetting resin of crosslinkability is mentioned, for example. Examples of the photocurable resin include epoxy-acrylic acid resins (acrylic acid derivative adducts of epoxy compounds) or urethane-acrylic acid resins (acrylic acid derivative adducts of urethane compounds). The base resins may be used alone or in combination of two or more.

  The base resin contained in the charge generation layer is preferably different from the binder resin contained in the charge transport layer. If the base resin is different from the binder resin, the base resin does not easily dissolve in the solvent used for the charge transport layer, and the base resin of the charge generation layer does not easily dissolve in forming the charge transport layer, and a uniform charge generation layer is formed. Because it is easy. Generally, in the manufacture of a photoreceptor, for example, a charge generation layer is formed on a conductive substrate, and a charge transport layer is formed on the charge generation layer. Therefore, when forming the charge transport layer, the charge transport layer coating solution is applied onto the charge generation layer.

<7. Additives>
The photosensitive layer of the photoreceptor may contain various additives, if necessary. As the additive, for example, an antidegradant (more specifically, an antioxidant, a radical scavenger, a quencher, an ultraviolet absorber, etc.), an electron acceptor compound, a softener, a surface modifier, an extender, These include thickeners, dispersion stabilizers, waxes, donors, surfactants, plasticizers, sensitizers, or leveling agents. Examples of the antioxidant include hindered phenols (more specifically, di (tert-butyl) p-cresol and the like), hindered amines, paraphenylenediamines, arylalkanes, spirochromans, spiroindanones or derivatives thereof, organic Sulfur compounds or organic phosphorus compounds can be mentioned.

<8. Middle layer>
The intermediate layer (undercoat layer) contains, for example, inorganic particles and a resin (interlayer resin) used for the intermediate layer. By the presence of the intermediate layer, it is considered that the flow of current generated when the photosensitive member is exposed can be smoothed and the increase in resistance can be suppressed while maintaining the insulation state to the extent that the occurrence of leakage can be suppressed.

  As the inorganic particles, for example, metals (more specifically, aluminum, iron or copper), metal oxides (more specifically, titanium oxide, alumina, zirconium oxide, tin oxide or zinc oxide etc.) Examples include particles or particles of nonmetallic oxides (more specifically, silica etc.). One of these inorganic particles may be used alone, or two or more thereof may be used in combination.

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

<9. Method of manufacturing photoreceptor>
The photoreceptor is manufactured, for example, as follows. First, a coating solution for charge generation layer and a coating solution for charge transport layer are prepared. A charge generation layer is formed by applying a charge generation layer coating solution on a conductive substrate and drying. Subsequently, the charge transport layer coating solution is applied onto the charge generation layer and dried to form a charge transport layer. Thus, a photosensitive member is manufactured.

  The charge generating layer coating solution is prepared by dissolving or dispersing the charge generating agent and the components (eg, base resin and various additives) added as needed in a solvent. Triarylamine hydrazone derivative (1) or (2) as hole transport agent, polycarbonate resin (3) as binder resin, and optional components (eg, electron acceptor compound, and various additives) The charge transport layer coating solution is prepared by dissolving or dispersing the compound in a solvent.

  The solvent contained in the coating solution for the charge generation layer and the coating solution for the charge transport layer (hereinafter sometimes referred to as the coating solution) is not particularly limited as long as each component contained in the coating solution can be dissolved or dispersed. . Examples of solvents include alcohols (eg methanol, ethanol, isopropanol or butanol), aliphatic hydrocarbons (eg n-hexane, octane or cyclohexane), aromatic hydrocarbons (eg benzene, toluene or xylene) ), Halogenated hydrocarbons (for example, dichloromethane, dichloroethane, carbon tetrachloride or chlorobenzene), ethers (for example, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or propylene glycol monomethyl ether), ketones (for example) For example, acetone, methyl ethyl ketone or cyclohexanone), esters (eg, ethyl acetate or methyl acetate), dimethyl formaldehyde, Chill formamide, or dimethyl sulfoxide. These solvents are used singly or in combination of two or more. In order to improve the workability at the time of production of the photosensitive member, it is preferable to use a non-halogen solvent (a solvent other than a halogenated hydrocarbon) as the solvent.

  The coating solution is prepared by mixing the components and dispersing in a solvent. For mixing or dispersing, for example, a bead mill, roll mill, ball mill, attritor, paint shaker, or 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 it is a method capable of uniformly applying the coating solution on the conductive substrate. As a coating method, a dip coating method, a spray coating method, a spin coating method, or a bar coating method is mentioned, for example.

  The method for drying the coating solution is not particularly limited as long as the solvent in the coating solution can be evaporated. For example, the method of heat-processing (hot-air drying) using a high temperature dryer or a reduced-pressure dryer is mentioned. The heat treatment conditions are, for example, a temperature of 40 ° C. to 150 ° C., and a time of 3 minutes to 120 minutes.

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

  The photosensitive member according to the present embodiment has been described above. According to the photosensitive member of the present embodiment, the electrical characteristics of the photosensitive member can be improved.

  Hereinafter, the present invention will be more specifically described using examples. However, the present invention is not at all limited to the scope of the examples.

<1. Material of Photoreceptor>
As materials for forming the charge generation layer and charge transport layer, the following hole transfer agent, charge generation agent, and binder resin were prepared.

[1-1. Hole transport agent]
Triarylamine hydrazone derivatives (HT-1) to (HT-7) were prepared as hole transport agents. The triarylamine hydrazone derivatives (HT-1) to (HT-7) were produced by the following methods, respectively.

[1-1-1. Production of Triarylamine Hydrazone Derivative (HT-1)]
Reactions represented by reaction formulas (r-1) to (r-5) and reaction formulas (r-7) to (r-8) (hereinafter referred to as reactions (r-1) to (r-5) and reactions, respectively The triarylamine hydrazone derivative (HT-1) was synthesized according to (r-7) to (r-8). In the reactions (r-1) to (r-2), a diphenyl alkene derivative (1E) was obtained. In reactions (r-3) to (r-5), a hydrazone derivative (1 L) was obtained. Then, in the reactions (r-7) to (r-8), the triarylamine hydrazone derivative (HT-1) was obtained. Hereinafter, the synthesis method of the triarylamine hydrazone derivative (HT-1) will be described in detail.

[Diphenyl alkene derivative (1E)]
The diphenyl alkene derivative (1E) was synthesized according to the reactions (r-1) to (r-2).

(Synthesis of phosphonate derivative (1C))
In the reaction (r-1), the benzene derivative (1A) (16.1 g, 0.1 mol) and triethyl phosphite (25 g, 0.15 mol) represented by the chemical formula (B) are added to a 200 mL flask And stirred for 8 hours at 180 ° C., and then cooled to room temperature. Thereafter, unreacted or remaining triethyl phosphite was distilled off under reduced pressure to obtain a phosphonate derivative (1C) as a white liquid. The yield of the phosphonate derivative (1C) from the benzene derivative (1A) was 24.1 g (yield: 92 mol%).

(Synthesis of diphenyl alkene derivative (1E))
In the reaction (r-2), the obtained phosphonate derivative (1C) (13 g, 0.05 mol) was added at 0 ° C. to a 500 mL two-necked flask. The inside of the flask was replaced with argon gas. After that, dry tetrahydrofuran (100 mL) and 28% sodium methoxide (9.3 g, 0.05 mol) were added to the flask and stirred for 30 minutes. Then, the aldehyde derivative (1D) (7 g, 0.05 mol) in dry tetrahydrofuran (300 mL) was added and stirred at room temperature for 12 hours. The resulting mixture was poured into ion exchanged water and extracted with toluene. The obtained organic layer was washed 5 times with ion exchanged water, dried over anhydrous sodium sulfate, and the solvent was evaporated. The resulting residue was purified with toluene / methanol (20 mL / 100 mL) to give diphenyl alkene derivative (1E) as white crystals. The yield from the phosphonate derivative (1C) of the diphenyl alkene derivative (1E) was 9.8 g (yield: 80 mol%).

[Hydrazone derivative (1 L)]
The hydrazone derivative (1 L) was synthesized according to the reactions (r-3) to (r-5).

(Synthesis of phosphonate derivative (1G))
A phosphonate derivative (1G) is obtained from the benzene derivative (1F) and triethyl phosphite represented by the chemical formula (B) according to the reaction (r-3) by the same method as the synthesis of the phosphonate derivative (1C) described above. The

(Synthesis of diphenyl ethene derivative (1J))
In the reaction (r-4), the obtained phosphonate derivative (1G) (13 g, 0.05 mol) was added at 0 ° C. to a 500 mL two-necked flask. The inside of the flask was replaced with argon gas. After that, dry tetrahydrofuran (100 mL) and 28% sodium methoxide (9.3 g, 0.05 mol) were added to the flask and stirred for 30 minutes. Thereafter, terephthalaldehyde (13.4 g, 0.1 mol) represented by the chemical formula (H) in dry tetrahydrofuran (300 mL) was added, and the mixture was stirred at room temperature for 12 hours. The resulting mixture was poured into ion exchanged water and extracted with toluene. The obtained organic layer was washed 5 times with ion exchanged water, dried over anhydrous sodium sulfate, and the solvent was evaporated. The resulting residue was purified with toluene / methanol (20 mL / 100 mL) to give diphenyl ethene derivative (1J) as white crystals. The yield of the diphenylethene derivative (1J) from the phosphonate derivative (1G) was 6.5 g (yield: 56 mol%).

(Synthesis of Hydrazone Derivative (1 L))
In the reaction (r-5), 11 g (0.045 mol) of diphenylethene derivative (1J), 10 g (0.045 mol) of diphenylhydrazine hydrochloride (1K), and 100 mL of toluene are charged into a flask, and a toluene solution is prepared. Was prepared. Further, 0.0045 molar equivalent of p-toluenesulfonic acid was added to the prepared toluene solution. The flask was set in an apparatus equipped with a Dean-Stark reaction tube, dehydrated and refluxed for 4 hours. After the reaction, the contents of the flask were added to ion exchanged water and extracted with toluene. The obtained organic layer (toluene) was washed 5 times with ion exchanged water, dried using anhydrous sodium sulfate, and the solvent was evaporated. As a result, a residue was obtained. The obtained residue was crystallized with toluene / ethanol (volume ratio V / V = 1/9) to obtain a hydrazone derivative (1 L) as white crystals. The yield of the hydrazone derivative (1 L) from the diphenyl ethene derivative (1 J) was 12.5 g (67 mol% yield).

[Triarylamine hydrazone derivative (HT-1)]
The triarylamine hydrazone derivative (HT-1) was synthesized according to the reactions (r-7) to (r-8).

In the reaction (r-7), 5.2 g (0.02 mol) of the diphenyl alkene derivative (1E) obtained in the reaction (r-2), 0.0662 g (0.000189 mol) of tricyclohexylphosphine, tris in a three-necked flask (Dibenzylideneacetone) 0.084 g (0.0000944 mol) of dipalladium (0), 4 g (0.042 mol) of sodium t-butoxide, 0.24 g (0.010 mol) of lithium amide (LiNH ₂ ), and distilled о− Xylene (500 mL) was added. The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The resulting residue was crystallized with chloroform / hexane (volume ratio V / V = 1/1) to obtain an intermediate product (amine derivative (1 M)) of the triarylamine hydrazone derivative (HT-1). The amine derivative (1M) is not described in Reaction Formulas (r-7) to (r-8). The yield of the obtained amine derivative (1M) from the diphenyl alkene derivative (1E) was 2.7 g (yield: 61 mol%).

In the reaction (r-8), the amine derivative (1 M) (2.6 g, 0.006 mol) obtained in the reaction (r-7) and the hydrazone derivative obtained in the reaction (r-5) were added to a three-necked flask 1 L) (2.4 g, 0.006 mol), tricyclohexylphosphine (0.020 543 g, 5.87 × 10 ^-5 mol), tris (dibenzylideneacetone) dipalladium (0) (0.026853 g, 2.93 × 10 ^-5 mol), sodium tert-butoxide (1 g, 0.010 mol) and distilled r-xylene (200 mL) were added. The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The resulting residue was crystallized using chloroform / hexane (volume ratio V / V = 1/1) as a developing solvent to obtain a triarylamine hydrazone derivative (HT-1). The yield of the triarylhydrazone derivative (HT-1) from the amine derivative (1M) was 3.1 g (yield: 66 mol%).

[1-1-2. Preparation of triarylamine hydrazone derivatives (HT-2) to (HT-3) and (HT-6)]
Triarylamine hydrazone derivatives (HT-2) to (HT-3) and (HT-6) were prepared in the same manner as in the preparation of triarylamine hydrazone derivative (HT-1) except that the following points were changed. Each was manufactured. In addition, the amount of substance of each reactant (Reactant) used in the production of triarylamine hydrazone derivatives (HT-2) to (HT-3) and (HT-6) is triarylamine unless otherwise specified. It is the same as the substance mass of the corresponding reactant in the production of the hydrazone derivative (HT-1).

Table 1 shows the addition amounts of diphenyl alkene derivative (E) and LiNH ₂ , their reaction ratio, and the yield and yield of amine derivative (M). The diphenyl alkene derivative (1E) used in the reaction (r-7) was changed to any of diphenyl alkene derivatives (2E) to (4E). As a result, any of amine derivatives (2M) to (4M) was obtained instead of the intermediate amine derivative (1M). In Table 1, the reaction ratio indicates the ratio of the substance weight of diphenyl alkene derivative (E) and LiNH _{2 in} the reaction (r-7) (the substance weight of diphenyl alkene derivative (E): the substance weight of lithium amide). The structures of diphenyl alkene derivatives (2E) to (4E) are shown below.

  Table 2 shows the addition amounts of the amine derivative (M) and the hydrazone derivative (L), their reaction ratio, and the yield and yield of the triarylamine hydrazone derivative (1). The amine derivative (1M) used in the reaction (r-8) was changed to any of amine derivatives (2M) to (4M). As a result, triarylamine hydrazone derivatives (HT-2) to (HT-3) and (HT-6) were obtained instead of the triarylamine hydrazone derivative (HT-1). In Table 2, the reaction ratio is the ratio of the substance mass of the amine derivative (M) and the hydrazone derivative (L) in the reaction (r-8) (the substance mass of the amine derivative (M): the substance mass of the hydrazone derivative (L)) Indicates

(Synthesis of diphenyl alkene derivatives (2E) and (4E))
The diphenyl alkene derivatives (2E) and (4E) used in the reaction (r-7) were produced by the following method. Table 3 shows the addition amounts of phosphonate derivative (C) and aldehyde derivative (D), their reaction ratio, and the yield and yield of diphenyl alkene derivative (E). The phosphonate derivative (1C) used in the reaction (r-2) was changed to a phosphonate derivative (2C) or (4C). As a result, diphenyl alkene derivative (2E) or (4E) was obtained instead of diphenyl alkene derivative (1E). In Table 3, the reaction ratio is the ratio of the substance mass of the phosphonate derivative (C) and the aldehyde derivative (D) in the reaction (r-2) (the substance mass of the phosphonate derivative (C): the substance mass of the aldehyde derivative (D)) Indicates The structures of aldehyde derivatives (2D) and (4D) are shown below, respectively.

(Synthesis of diphenyl alkene derivative (3E))
The diphenyl alkene derivative (3E) used in the reaction (r-7) was synthesized according to the reaction (r-2 ′).

  In the reaction (r-2 '), the obtained phosphonate derivative (3C') (13 g, 0.05 mol) was added at 0 ° C to a 500 mL two-necked flask. The inside of the flask was replaced with argon gas. After that, dry tetrahydrofuran (100 mL) and 28% sodium methoxide (9.3 g, 0.05 mol) were added to the flask and stirred for 30 minutes. Then, the aldehyde derivative (3D ') (6 g, 0.05 mol) in dry tetrahydrofuran (300 mL) was added and stirred at room temperature for 12 hours. The resulting mixture was poured into ion exchanged water and extracted with toluene. The obtained organic layer was washed 5 times with ion exchanged water, dried over anhydrous sodium sulfate, and the solvent was evaporated. The resulting residue was purified with toluene / methanol (20 mL / 100 mL) to give diphenyl alkene derivative (3E) as white crystals. The yield from the phosphonate derivative (3C ') of the diphenyl alkene derivative (3E) was 9.6 g (yield: 88 mol%).

(Synthesis of phosphonate derivative (3C '))
According to the reaction (r-1 '), the phosphonate derivative (3C') used in the reaction (r-2 ') was synthesized.

  In the reaction (r-1 ′), in a 200 mL flask, benzene derivative (3A ′) (15.2 g, 0.1 mol) and triethyl phosphite (25 g, 0.15 mol represented by the chemical formula (B) And stirred for 8 hours at 180 ° C., and then cooled to room temperature. Thereafter, unreacted or remaining triethyl phosphite was distilled off under reduced pressure to obtain a phosphonate derivative (3C ') as a white liquid. The yield of the phosphonate derivative (3C ') from the benzene derivative (3A') was 23.5 g (yield: 92 mol%).

[1-1-3. Production of Triarylamine Hydrazone Derivative (HT-5)]
Triarylamines according to the reactions represented by reaction formulas (r-7 ′) to (r-8 ′) (hereinafter sometimes referred to as reactions (r-7 ′) to (r-8 ′), respectively) A hydrazone derivative (HT-5) was produced.

In the reaction (r-7 '), in a three-necked flask, 8.2 g (0.02 mol) of the hydrazone derivative (1 L) obtained in the reaction (r-5), 0.0662 g (0.000189 mol) of tricyclohexylphosphine, tris (Dibenzylideneacetone) 0.084 g (0.0000944 mol) of dipalladium (0), 4 g (0.042 mol) of sodium tert-butoxide, 0.24 g (0.010 mol) of lithium amide (LiNH ₂ ), and distilled о− Xylene (500 mL) was added. The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The obtained residue was crystallized with chloroform / hexane (volume ratio V / V = 1/1) to obtain an intermediate product (amine derivative (5N)) of the triarylamine hydrazone derivative (HT-5). The amine derivative (5N) is not described in Reaction Formulas (r-7 ') to (r-8'). The yield from the hydrazone derivative (1 L) of the obtained amine derivative (5 N) was 4.6 g (yield: 58 mol%).

In the reaction (r-8 '), the amine derivative (5N) (4.6 g, 0.006 mol) obtained in the reaction (r-7') and the diphenyl obtained in the reaction (r-2) were added to a three-necked flask. Alkene derivative (2E) (1.3 g, 0.006 mol), tricyclohexylphosphine (0.020 543 g, 5.87 × 10 ^-5 mol), tris (dibenzylideneacetone) dipalladium (0) (0.026853 g, 2 .93 × 10 ^-5 mol), sodium tert-butoxide (1 g, 0.010 mol), and distilled о-xylene (200 mL) were added. The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The resulting residue was crystallized using chloroform / hexane (volume ratio V / V = 1/1) as a developing solvent to obtain a triarylamine hydrazone derivative (HT-5). The yield of the triarylamine hydrazone derivative (HT-5) from the amine derivative (5N) was 3.8 g (yield: 69 mol%).

[1-1-4. Production of Triarylamine Hydrazone Derivative (HT-7)]
The triarylamine hydrazone derivative (HT-7) was synthesized according to the reaction represented by the following reaction formula.

In a three-necked flask, 12.3 g (0.03 mol) of the hydrazone derivative (1 L) obtained in the reaction (r-5), 0.087 g (0.000248 mol) of tricyclohexylphosphine, tris (dibenzylideneacetone) dipalladium (0) ) 0.113 g (0.0000123 mol), sodium tert-butoxide 5.0 g (0.053 mol), lithium amide (LiNH ₂ ) 0.24 g (0.010 mol), and distilled о-xylene (500 mL) were added . The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The obtained residue was purified by silica gel column chromatography using chloroform / hexane (volume ratio V / V = 1/1) as a developing solvent to obtain a triarylamine hydrazone derivative (HT-7). The yield of the triarylamine hydrazone derivative (HT-7) was 7.7 g (yield: 65 mol%).

[1-1-5. Production of Triarylamine Hydrazone Derivative (HT-4)]
A triarylamine hydrazone derivative (HT-4) was produced according to the reaction represented by the reaction formula (r-9) (hereinafter sometimes referred to as reaction (r-9)).

In the reaction (r-9), diphenylamine derivative (1Q) (3.20 g, 0.015 mol), hydrazone derivative (1P) (6.13 g, 0.015 mol), tricyclohexylphosphine (0.020543 g) in a three-necked flask. 5.87 × 10 ^-5 mol), tris (dibenzylideneacetone) dipalladium (0) (0.026853 g, 2.93 × 10 ^-5 mol), sodium tert-butoxide (1 g, 0.010 mol), and distillation R-xylene (200 mL) was added. In addition, hydrazone derivative (1P) was synthesize | combined by reaction (r-5) similarly to hydrazone derivative (1 L). The inside of the flask was replaced with argon gas. The flask contents were then stirred at 120 ° C. for 5 hours and cooled to room temperature. The resulting mixture was washed three times with ion exchange water to obtain an organic layer. Anhydrous sodium sulfate and activated clay were added to the organic layer, and drying treatment and adsorption treatment were performed. Thereafter, the obtained organic layer was evaporated under reduced pressure to remove о-xylene. The resulting residue was crystallized using chloroform / hexane (volume ratio V / V = 1/1) as a developing solvent to obtain a triarylamine hydrazone derivative (HT-4). The yield of the triarylhydrazone derivative (HT-4) from the diphenylamine derivative (1Q) was 5.3 g (yield: 60 mol%).

Next, ¹ H-NMR spectra of the produced triarylamine hydrazone derivatives (HT-1) to (HT-7) were measured using a proton nuclear magnetic resonance spectrometer (manufactured by JASCO Corporation, 300 MHz). CDCl ₃ was used as a solvent. Tetramethylsilane (TMS) was used as an internal standard sample. Among these, triarylamine hydrazone derivatives (HT-4) and (HT-2) are mentioned as a representative example.

FIG. 2 shows the ¹ H-NMR spectrum of the triarylamine hydrazone derivative (HT-4). In FIG. 2, the vertical axis represents signal intensity, and the horizontal axis represents chemical shift value (ppm). The chemical shift values of the triarylamine hydrazone derivatives (HT-4) and (HT-2) are shown below.
Triarylamine hydrazone derivative (HT-4): ¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.55 to 7.59 (m, 2H), 7.38 to 7.46 (m, 6H), 7 .30-7.35 (m, 2H), 7.13-7.22 (m, 7H), 6.90-7.10 (m, 10H), 6.80-6.86 (m, 2H) , 3.80 (s, 3H), 2.31 (s, 3H).
Triarylamine hydrazone derivative (HT-2): ¹ H-NMR (300 MHz, CDCl ₃ ) δ = 7.57-7.61 (m, 5H), 7.37-7.48 (m, 15H), 7 .00-7.34 (m, 23H).

It was confirmed by ¹ H-NMR spectrum and chemical shift that triarylamine hydrazone derivatives (HT-4) and (HT-2) were obtained. Similarly to the other triarylamine hydrazone derivatives (HT-1), (HT-3), and (HT-5) to (HT-7), triarylamines by ¹ H-NMR spectrum and chemical shift value It was confirmed that the hydrazone derivatives (HT-1), (HT-3), and (HT-5) to (HT-7) were obtained, respectively. The ¹ H-NMR spectrum shows only the triarylamine hydrazone derivative (HT-4).

[1-1-6. Preparation of Compounds (HT-A) to (HT-B)]
A compound represented by the chemical formula (HT-A) as the hole transport agent (hereinafter sometimes referred to as a compound (HT-A)), and a compound represented by the chemical formula (HT-B) (hereinafter referred to as the compound Prepared as HT-B).

[1-2. Charge generator]
The above-described compound (C-1) and compound (C-2) were prepared as charge generating agents. The compound (C-1) was a metal-free phthalocyanine (X-type metal-free phthalocyanine) represented by the chemical formula (C-1). Moreover, the crystal structure of a compound (C-1) was X-type. The compound (C-2) was a titanyl phthalocyanine (Y-type titanyl phthalocyanine) represented by a chemical formula (C-2). Moreover, the crystal structure of a compound (C-2) was Y-type. In addition, the X-ray diffraction spectrum of the compound (C-2) had a main peak at a Bragg angle 2θ ± 0.2 ° = 27.2 °.

[1-3. Binder resin]
The above-mentioned polycarbonate resins (Resin-1) to (Resin-4) were prepared as binder resins. The viscosity average molecular weights of polycarbonate resins (Resin-1) to (Resin-4) were 45,000, 49, 100, 51, 200, and 47, 800, respectively. Furthermore, binder resin (It may describe as binder resin (Resin-5) hereafter) which has a repeating unit represented by Chemical formula (Resin-5) as binder resin was prepared. The viscosity average molecular weight of the polycarbonate resin (Resin-5) was 50,500.

<2. Production of photoconductor>
[2-1. Production of photoconductor]
Photosensitive members (A-1) to (A-10) and photosensitive members (B-1) to (B-3) were manufactured using materials for forming a photosensitive layer.

[2-1-1. Production of Photoreceptor (A-1)]
(Formation of undercoat layer)
First, surface-treated titanium oxide ("prototype SMT-02" manufactured by Tayca Corporation, number average primary particle diameter 10 nm) was prepared. Specifically, the surface was treated with alumina and silica, and further, the surface-treated titanium oxide was wet-dispersed to prepare a surface-treated with methyl hydrogen polysiloxane. Next, a quaternary copolymerized polyamide resin of surface-treated titanium oxide (2 parts by mass), polyamide 6, polyamide 12, polyamide 66, and polyamide 610 (Toray Industries, Inc. "Nylon resin Amiran (registered trademark) CM 8000") (1 part by mass) was added to a solvent containing methanol (10 parts by mass), butanol (1 part by mass), and toluene (1 part by mass). These were mixed for 5 hours using a bead mill to disperse the materials in the solvent. Thus, a coating solution for undercoat layer was prepared.

  The obtained undercoat layer coating solution was filtered using a filter with an aperture of 5 μm. Thereafter, a coating solution for an intermediate layer was applied to the surface of an aluminum drum-shaped support (diameter 30 mm, total length 246 mm) as a conductive substrate using a dip coating method. Subsequently, the applied coating solution for undercoat layer was dried at 130 ° C. for 30 minutes to form an undercoat layer (film thickness 2 μm) on the conductive substrate (drum-like support).

(Formation of charge generation layer)
Next, a compound (C-2) (Y-type titanyl phthalocyanine) (1.5 parts by mass) as a charge generating agent, and a polyvinyl acetal resin ("S-LEC BX-5" manufactured by Sekisui Chemical Co., Ltd.) as a binder resin (1 Parts by mass) were added to a mixed solvent of 40 parts by mass of propylene glycol monomethyl ether and 40 parts by mass of tetrahydrofuran as a solvent (dispersion medium). These were mixed for 2 hours using a bead mill, and the materials were dispersed in a solvent to prepare a coating solution for charge generation layer. The obtained charge generation layer coating solution was filtered using a filter with an aperture of 3 μm. Next, the obtained filtrate was applied onto the undercoat layer formed as described above using dip coating, and dried at 50 ° C. for 5 minutes. Thereby, a charge generation layer (film thickness 0.3 μm) was formed on the undercoat layer.

(Formation of charge transport layer)
Next, a triarylamine hydrazone derivative (HT-1) (50 parts by mass) as a hole transfer agent, and a phenol-based antioxidant as an additive (“Irganox (registered trademark) 1010” manufactured by BASF Corp.) ( 2 parts by mass), polycarbonate resin (Resin-1) (viscosity average molecular weight 45,000) as binder resin (100 parts by mass), tetrahydrofuran (THF) as solvent (560 parts by mass) and toluene (140 parts by mass) Was added to the mixed solvent of The mixing ratio of THF to toluene was 560/140 = 8/2 in volume ratio (THF / toluene). These were mixed for 12 hours using a circulating ultrasonic dispersion device to disperse or dissolve the materials in the solvent. As a result, a coating solution for charge transport layer was prepared. The prepared charge transport layer coating solution is applied onto the charge generation layer in the same manner as the charge generation layer coating solution, and dried at 120 ° C. for 60 minutes to form a charge transport layer having a thickness of 30 μm. (A-1) was produced.

[2-1-2. Production of Photoreceptors (A-2) to (A-10) and Photoreceptors (B-1) to (B-3)]
The photosensitive members (A-2) to (A-10) and the photosensitive members (B-1) to (B-3) were produced in the same manner as in the production of the photosensitive member (A-1) except that the following points were changed. ) Were produced respectively. The triarylamine hydrazone derivative (HT-1) as a hole transport agent used in the production of the photosensitive member (A-1) was changed to a hole transport agent of the type shown in Table 4. Table 4 shows the structures of photoreceptors (A-1) to (A-10) and photoreceptors (B-1) to (B-3). In Table 4, HTM indicates a hole transfer agent. In Table 4, HT-1 to HT-7 and HT-A to HT-B in the column HTM represent triarylamine hydrazone derivatives (HT-1) to (HT-7) and compounds (HT-A) to (HT-B) is shown.

<3. Evaluation of Electrical Characteristics of Photoreceptor>
The electrical characteristics of each of the manufactured photosensitive members (A-1) to (A-10) and the photosensitive members (B-1) to (B-3) were evaluated. Evaluation of the electrical property was performed under the environment of temperature 23 ° C. and humidity 50% RH. First, the surface of the photosensitive member was charged to -600 V using a drum sensitivity tester (manufactured by Gentec Co., Ltd.). Next, monochromatic light (wavelength 780 nm, half width 20 nm, light energy 1.5 μJ / cm ² ) was extracted from white light of the halogen lamp using a band pass filter. The extracted monochromatic light was irradiated to the surface of the photoreceptor. The surface potential of the photoreceptor was measured 66.7 milliseconds after the end of the irradiation. The measured surface potential was taken as the sensitivity potential (V _L , unit V). The measured sensitivity potentials (V _L ) of the photosensitive members are shown in Table 4. The smaller the absolute value of the sensitivity potential (V _L ), the better the electrical characteristics of the photosensitive member.

<4. Evaluation of abrasion resistance of photoreceptor>
An aluminum pipe (diameter: 78 mm) was used for the charge transport layer coating liquid prepared in the production of any of the photosensitive members (A-1) to (A-10) and the photosensitive members (B-1) to (B-3). It applied to the polypropylene sheet (thickness 0.3 mm) wound around. This was dried at 120 ° C. for 60 minutes to prepare a sheet for a wear evaluation test in which a charge transport layer having a thickness of 30 μm was formed.

  The charge transport layer was peeled off from the polypropylene sheet and attached to Wheel S-36 (manufactured by Taber) to prepare a sample. The prepared sample is set on a rotary abrasion tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a wear evaluation test is performed using a wear ring CS-10 (manufactured by Taber) under a load of 750 gf and a rotation speed of 60 rpm for 1,000 revolutions. Carried out. Abrasion loss (mg / 1000 revolutions) which is a mass change of the sample before and after the abrasion evaluation test was measured. Table 4 shows wear loss. The smaller the wear loss, the better the wear resistance of the photoreceptor.

  As shown in Table 4, in the photosensitive members (A-1) to (A-10), the charge transport layer is any of triarylamine hydrazone derivatives (HT-1) to (HT-7) as a hole transport agent. It contained one kind. These triarylamine hydrazone derivatives (HT-1) to (HT-7) were triarylamine hydrazone derivatives represented by the general formula (1) or (2). In the photoreceptors (A-1) to (A-10), the charge transport layer contained any one of polycarbonate resins (Resin-1) to (Resin-4) as a binder resin. These polycarbonate resins (Resin-1) to (Resin-4) were polycarbonate resins represented by General Formula (3).

  In the photosensitive members (A-1) to (A-10), the sensitivity potential was -105 V or more and -85 V or less, and the abrasion loss was 8.8 mg or more and 11.6 mg or less.

  As shown in Table 4, in the photoreceptors (B-1) to (B-2), the charge transport layer respectively contains any one of the compounds (HT-A) to (HT-B) as a hole transport agent. It contained. Compounds (HT-A) to (HT-B) were neither of the triarylamine hydrazone derivatives represented by the general formulas (1) and (2). In the photoreceptor (B-3), the charge transport layer contained a binder resin (Resin-5) as a binder resin. Binder resin (Resin-5) It was not polycarbonate resin represented by General formula (3).

  The photosensitive members (B-1) to (B-2) had sensitivity potentials of -135 V and -138 V, respectively. "-" In Table 4 shows that it did not measure. In the case of the photosensitive member (B-3), the sensitivity potential was −88 V and the abrasion loss was 15.0 mg.

  Therefore, it is clear that the photosensitive members (A-1) to (A-10) have both the electrical characteristics (sensitivity characteristics) and the abrasion resistance as compared with the photosensitive members (B-1) to (B-3). is there.

  Table 5 shows the relationship between the number of double bonds in the diphenyl alkenyl moiety of the triarylamine hydrazone derivative and the sensitivity potential of the photoreceptor. The number of double bonds in Table 5 indicates the number of double bonds in alkenyl in the diphenyl alkenyl moiety of the triarylamine hydrazone derivative. In the triarylamine hydrazone derivative (HT-4), although there was no diphenyl alkenyl site, the number of double bonds was counted as zero. As shown in Table 5, in the photoreceptors (A-1) to (A-4), the sensitivity potential of the photoreceptor increased as the number of double bonds of the triarylamine hydrazone derivative increased. Therefore, it was shown that the sensitivity characteristics of the photosensitive member were improved as the spatial spread of the π-conjugated system of the triarylamine hydrazone derivative was increased. On the other hand, as shown in Table 5, in the photoreceptors (A-1) to (A-4), as the number of double bonds of the triarylamine hydrazone derivative decreases, the abrasion loss of the photoreceptor decreases. Therefore, it was shown that the abrasion resistance of the photoreceptor was improved as the spatial extent of the π conjugated system of the triarylamine hydrazone derivative was reduced.

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

1 Electrophotographic photosensitive member 3 Photosensitive layer 3a Charge generation layer 3b Charge transport layer

Claims (7)

An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer,
The photosensitive layer includes a charge generation layer and a charge transport layer,
The charge generation layer contains a charge generation agent,
The charge transport layer contains a hole transport agent and a binder resin,
The hole transfer agent includes a triarylamine hydrazone derivative represented by the following general formula (1 ) ,
The electrophotographic photosensitive member, wherein the binder resin comprises a polycarbonate resin represented by the following general formula (3).

In the general formula (1),
R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an alkoxy having 1 to 6 carbon atoms which may have a substituent A group or an aryl group having 6 to 14 carbon atoms which may have a substituent,
n represents 2 or 3, k represents an integer of 1 or more and 3 or less,
u and m each independently represent an integer of 0 or more and 5 or less,
When k represents 1, R ¹ bonded to different phenyl groups may be identical to or different from each other,
R ² bonded to different phenyl groups may be identical to or different from each other,
When u represents an integer of 2 or more, plural R ¹ bonded to the same phenyl group may be the same as or different from each other,
When m represents an integer of 2 or more, plural R ² bonded to the same phenyl group may be the same as or different from each other ,
During the previous following general formula (3),
R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 14 carbon atoms,
R ⁷ and R ⁸ may represent a cycloalkylidene group having 3 to 8 carbon atoms which is formed by bonding to each other. In the general formula (1),
R ¹ represents an alkyl group having 1 to 3 carbon atoms,
u represents 0 or 1 and
The electrophotographic photosensitive member according to claim 1, wherein m represents 0. In the general formula (3),
R ⁷ and R ⁸ represent a cycloalkylidene group having 1 to 4 carbon atoms an alkyl group, or a bonded carbon atom number of 5 or more 7 formed by following one another, electrophotography according to claim 1 or 2 Photoconductor. In the general formula (3),
R ⁷ and R ⁸ represents a bond to the carbon atoms which is formed by 5 to 7 cycloalkylidene group together electrophotographic photosensitive member according to any one of claims 1-3. The electrophotographic photosensitive member according to any one of claims 1 to 4 , wherein the charge generating agent contains Y-type titanyl phthalocyanine.   An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer,
  The photosensitive layer includes a charge generation layer and a charge transport layer,
  The charge generation layer contains a charge generation agent,
  The charge transport layer contains a hole transport agent and a binder resin,
  The hole transfer agent includes a triarylamine hydrazone derivative represented by the following general formula (1 ′),
  The electrophotographic photosensitive member, wherein the binder resin comprises a polycarbonate resin represented by the following general formula (3 ′).

  In the general formula (1 '),
  R ¹ And R ² Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or a substituent And an aryl group having 6 to 14 carbon atoms which may have
  n represents 1 and
  k represents an integer of 1 or more and 3 or less,
  u and m each independently represent an integer of 0 or more and 5 or less,
  When k represents 1, R bound to a different phenyl group ¹ May be identical to or different from each other,
  R bound to different phenyl groups ² May be identical to or different from each other,
  when u represents an integer of 2 or more, a plurality of R bound to the same phenyl group ¹ May be identical to or different from each other,
  when m represents an integer of 2 or more, a plurality of R bound to the same phenyl group ² May be identical to or different from each other,
  In the general formula (3 '),
  R ⁵ , R ⁶ , R ⁷ , And R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 14 carbon atoms,
  R ⁷ And R ⁸ And may be a cycloalkylidene group having 3 to 8 carbon atoms which is formed by bonding to each other.   An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer,
  The photosensitive layer includes a charge generation layer and a charge transport layer,
  The charge generation layer contains a charge generation agent,
  The charge transport layer contains a hole transport agent and a binder resin,
  The hole transfer agent includes a triarylamine hydrazone derivative represented by the following general formula (1 ′ ′),
  The electrophotographic photosensitive member, wherein the binder resin comprises a polycarbonate resin represented by the following general formula (3 ′ ′).

  In the general formula (1 ′ ′),
  R ¹ And R ² Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or a substituent And an aryl group having 6 to 14 carbon atoms which may have
  n represents an integer of 1 or more and 3 or less,
  k represents 1 and
  u and m each independently represent an integer of 0 or more and 5 or less,
  When k represents 1, R bound to a different phenyl group ¹ May be identical to or different from each other,
  R bound to different phenyl groups ² May be identical to or different from each other,
  when u represents an integer of 2 or more, a plurality of R bound to the same phenyl group ¹ May be identical to or different from each other,
  when m represents an integer of 2 or more, a plurality of R bound to the same phenyl group ² May be identical to or different from each other,
  In the general formula (3 ′ ′),
  R ⁵ , R ⁶ , R ⁷ , And R ⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 14 carbon atoms,
  R ⁷ And R ⁸ And may be a cycloalkylidene group having 3 to 8 carbon atoms which is formed by bonding to each other.

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