CN107643658B - Electrophotographic photoreceptor - Google Patents
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- CN107643658B CN107643658B CN201710564485.0A CN201710564485A CN107643658B CN 107643658 B CN107643658 B CN 107643658B CN 201710564485 A CN201710564485 A CN 201710564485A CN 107643658 B CN107643658 B CN 107643658B
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Abstract
The invention provides an electrophotographic photoreceptor. An electrophotographic photoreceptor includes a conductive substrate and a photosensitive layer. The photosensitive layer contains a charge generator, a hole transport agent, a benzoquinone methide derivative, and a binder resin. The benzoquinone methide derivative is represented by the general formula (1). R in the general formula (1)1、R2、R3And m is independently from R in the specification1、R2、R3And m have the same meaning. [ CHEM 1 ]
Description
Technical Field
The present invention relates to an electrophotographic photoreceptor.
Background
Electrophotographic photoreceptors are used in electrophotographic image forming apparatuses. The electrophotographic photoreceptor includes a photosensitive layer. Examples of the electrophotographic photoreceptor include a laminated electrophotographic photoreceptor and a single-layer electrophotographic photoreceptor. The photosensitive layer in the laminated electrophotographic photoreceptor is a charge generation layer having a charge generation function and a charge transport layer having a charge transport function. The photosensitive layer in the single-layer electrophotographic photoreceptor is a single-layer photosensitive layer having a charge generating function and a charge transporting function.
In the electrophotographic photoreceptor described in patent document 1, the photosensitive layer contains a compound represented by the chemical formula (E-2), for example.
[ CHEM 1 ]
[ patent document ]
Patent document 1: japanese patent laid-open publication No. 2005-173292
Disclosure of Invention
However, the electrophotographic photoreceptor described in patent document 1 has insufficient sensitivity characteristics.
The present invention has been made in view of the above problems, and an object thereof is to provide an electrophotographic photoreceptor having excellent sensitivity characteristics.
The electrophotographic photoreceptor of the present invention includes a conductive substrate and a photosensitive layer. The photosensitive layer contains: a charge generating agent, a hole transporting agent, a benzoquinone methide derivative, and a binder resin. The benzoquinone methide derivative is represented by the general formula (1).
[ CHEM 2 ]
In the general formula (1), R1Represents: general formula (2), C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl, nitro, C2-C7 alkoxycarbonyl or halogen atom. R1The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R1The C6-C14 aryl group represented by (a) may have a first substituent. R2And R3Independently of each other, represents: C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl or halogen atom. R2And R3The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R2And R3The C6-C14 aryl group may have a second substituent. m represents an integer of 0 to 5 inclusive. When m represents an integer of 2 to 5 inclusive, a plurality of R1May be the same or different from each other.
[ CHEM 3 ]
In the general formula (2), R4And R5Independently of each other, represents: C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl or halogen atom. R4And R5The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R4And R5The C6-C14 aryl group represented by (a) may have a third substituent. The first substituent, the second substituent, and the third substituent are each independently represented by: a C1-C6 alkyl group which may have a C6-C14 aryl group; or a C1-C6 alkoxy group, a C6-C14 aryl group, a C1-C7 acyl group or a halogen atom. The C1-C6 alkyl group represented by the first substituent, the second substituent and the third substituent may also have a C6-C14 aryl group.
[ Effect of the invention ]
The electrophotographic photoreceptor of the present invention has excellent sensitivity characteristics.
Drawings
Fig. 1(a), 1(b) and 1(c) are schematic cross-sectional views each showing an example of an electrophotographic photoreceptor according to an embodiment of the present invention.
Fig. 2(a), 2(b) and 2(c) are schematic cross-sectional views respectively showing other examples of the electrophotographic photoreceptor according to the embodiment of the present invention.
FIG. 3 is a graph showing the infrared absorption spectrum of the benzoquinone methide derivative (1-1).
FIG. 4 is a graph showing the infrared absorption spectrum of the quinone methide derivatives (1-4).
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments in any way. The present invention can be implemented by appropriately changing the range of the object. Note that, although the description thereof may be omitted as appropriate, the gist of the present invention is not limited thereto.
Hereinafter, the compound and its derivatives may be collectively referred to by adding "class" to the compound name. When a "class" is added to a compound name to indicate a polymer name, the repeating unit indicating the polymer is derived from the compound or a derivative thereof.
Hereinafter, C1-C6 alkyl group, C1-C4 alkyl group, C1-C3 alkyl group, C1-C6 alkoxy group, C1-C7 acyl group, C2-C7 alkoxycarbonyl group, C2-C4 alkoxycarbonyl group, C6-C14 aryl group and halogen atom have the following meanings, respectively, unless otherwise specified.
The C1-C6 alkyl group is linear or branched and unsubstituted. Examples of the C1-C6 alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl or n-hexyl.
The C1-C4 alkyl group is linear or branched and unsubstituted. Examples of the C1-C4 alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl.
The C1-C3 alkyl group is linear or branched and unsubstituted. Examples of the C1-C3 alkyl group include: methyl, ethyl, n-propyl or isopropyl.
The C1-C6 alkoxy group is linear or branched and unsubstituted. Examples of the C1-C6 alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy or hexoxy.
The C1-C7 acyl group is linear or branched and unsubstituted. Examples of the C1-C7 acyl group include: formyl, methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, pentylcarbonyl, isopentylcarbonyl, neopentylcarbonyl, or n-hexylcarbonyl.
The C2-C7 alkoxycarbonyl group is linear or branched and unsubstituted. Examples of the C2-C7 alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl or hexyloxycarbonyl.
The C2-C4 alkoxycarbonyl group is linear or branched and unsubstituted. Examples of the C2-C4 alkoxycarbonyl group include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or isopropoxycarbonyl.
The C6-C14 aryl group is unsubstituted. C6-C14 aryl is, for example: C6-C14 unsubstituted aromatic monocyclic hydrocarbon group, C6-C14 unsubstituted aromatic condensed bicyclic hydrocarbon group or C6-C14 unsubstituted aromatic condensed tricyclic hydrocarbon group. Examples of the C6-C14 aryl group include: phenyl, naphthyl, anthryl or phenanthryl.
Examples of the halogen atom include: fluorine atom, chlorine atom, bromine atom or iodine atom.
Embodiments of the present invention relate to an electrophotographic photoreceptor (hereinafter, may be referred to as a photoreceptor). The photoreceptor according to the embodiment of the present invention is excellent in sensitivity characteristics. The reason is presumed as follows. The photoreceptor according to the present embodiment contains a benzoquinone methide derivative represented by the general formula (1) (hereinafter, sometimes referred to as benzoquinone methide derivative (1)). In the structure of the benzoquinone methide derivative (1), at least one benzoquinone methide moiety is bonded via an ester moietyAre bonded to a benzene ring. Therefore, the benzoquinone methide derivative (1) has a relatively large pi conjugated system. Therefore, in the benzoquinone methide derivative (1), the carrier (electron) acceptance and transmission properties are often excellent. Further, the benzoquinone methide derivative (1) has R2And R3. Then, the bond (single bond) of the benzoquinone methylated portion to the ester portion and the bond (single bond) of the ester portion to the benzene ring can be rotated. Therefore, the benzoquinone methide derivative (1) tends to be excellent in solubility in a solvent used for forming the photosensitive layer and dispersibility in the photosensitive layer. Therefore, the electrophotographic photoreceptor according to the present embodiment is considered to have excellent sensitivity characteristics.
The photoreceptor according to the present embodiment may be a single-layer type electrophotographic photoreceptor (hereinafter, referred to as a single-layer type photoreceptor) or a laminated type electrophotographic photoreceptor (hereinafter, referred to as a laminated type photoreceptor).
<1 > Single layer type photoreceptor
Hereinafter, a structure in the case where the photoreceptor 1 is a single-layer type photoreceptor will be described with reference to fig. 1(a), 1(b), and 1 (c). Fig. 1(a), 1(b), and 1(c) are schematic cross-sectional views each showing an example of the photoreceptor 1 according to the present embodiment.
As shown in fig. 1(a), a photoreceptor 1, which is a single-layer photoreceptor, includes a conductive substrate 2 and a photosensitive layer 3. In the single-layer photoreceptor, a single-layer photosensitive layer 3a is used as the photosensitive layer 3. The monolayer type photosensitive layer 3a is a photosensitive layer 3 of one layer.
As shown in fig. 1(b), the photoreceptor 1, which is a single-layer type photoreceptor, may include: a conductive substrate 2, a monolayer type photosensitive layer 3a, and an intermediate layer (undercoat layer) 4. The intermediate layer 4 is provided between the conductive substrate 2 and the monolayer photosensitive layer 3 a. As shown in fig. 1(c), a protective layer 5 may be provided on the monolayer photosensitive layer 3 a.
The thickness of the monolayer photosensitive layer 3a is not particularly limited as long as the function of the monolayer photosensitive layer can be sufficiently exhibited. The thickness of the monolayer type photosensitive layer 3a is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. The structure of the photoreceptor 1, which is a single-layer type photoreceptor, is described above with reference to fig. 1(a), 1(b), and 1 (c).
<2 > laminated photoreceptor
The structure of the laminated photoreceptor will be described below with reference to fig. 2(a), 2(b), and 2 (c). Fig. 2(a), 2(b), and 2(c) are schematic cross-sectional views respectively showing other examples of the photoreceptor according to the embodiment of the present invention.
As shown in fig. 2(a), a photoreceptor 1, which is a laminated photoreceptor, includes a conductive substrate 2 and a photosensitive layer 3. The photosensitive layer 3 includes a charge generation layer 3b and a charge transport layer 3 c. In order to improve the abrasion resistance of the laminated photoreceptor, it is preferable that: as shown in fig. 2(a), a charge generation layer 3b is provided on the conductive substrate 2, and a charge transport layer 3c is provided on the charge generation layer 3 b.
As shown in fig. 2(b), in the photoreceptor 1 which is a laminated photoreceptor, a charge transport layer 3c may be provided on the conductive substrate 2, and a charge generation layer 3b may be provided on the charge transport layer 3 c.
As shown in fig. 2(c), the photoreceptor 1, which is a laminated photoreceptor, may include: 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. The photosensitive layer 3 may be provided with a protective layer 5 (see fig. 1 (c)).
The thicknesses of the charge generation layer 3b and the charge transport layer 3c are not particularly limited as long as each layer can sufficiently exhibit its function. The thickness of the charge generation layer 3b is preferably 0.01 μm to 5 μm, and more preferably 0.1 μm to 3 μm. The thickness of the charge transport layer 3c is preferably 2 μm to 100 μm, and more preferably 5 μm to 50 μm.
The charge generation layer 3b in the photosensitive layer 3 contains a charge generator. The charge generation layer 3b may contain a binder resin for charge generation layer (hereinafter, may be referred to as a matrix resin). The charge generation layer 3b may contain various additives as needed. The structure of the photoreceptor 1, which is a laminated photoreceptor, is described above with reference to fig. 2(a), 2(b), and 2 (c).
The photosensitive layer contains: a charge generating agent, a hole transporting agent, a benzoquinone methide derivative, and a binder resin. The photosensitive layer may contain additives as necessary. Hereinafter, elements of the multilayer type photoreceptor and the single layer type photoreceptor will be described. A method for manufacturing the photoreceptor will be described.
<3 > conductive substrate >
The conductive substrate is not particularly limited as long as it can be used as a conductive substrate of a photoreceptor. The conductive substrate may be formed of a conductive material at least on the surface portion. An example of the conductive substrate is a conductive substrate formed of a conductive material. Another example of the conductive substrate is a conductive substrate coated with a conductive material. Examples of the conductive material include: aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, or indium. These conductive materials may be used alone, or two or more of them may be used in combination. Examples of the combination of two or more of them include: an alloy (more specifically, an aluminum alloy, stainless steel, brass, or the like). Among these conductive materials, aluminum or an aluminum alloy is preferable in terms of good charge transfer from the photosensitive layer to the conductive substrate.
The shape of the conductive substrate is appropriately selected according to the structure of the image forming apparatus. Examples of the shape of the conductive substrate include: sheet-like or drum-like. The thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.
<4. benzoquinone methide derivatives >
When the photoreceptor is a multilayer photoreceptor, the charge transport layer contains the benzoquinone methide derivative (1) as an electron acceptor compound. When the photoreceptor is a single-layer photoreceptor, the single-layer photosensitive layer contains a benzoquinone methide derivative (1) as an electron-transporting agent. Since the photosensitive layer contains the benzoquinone methide derivative (1), the photoreceptor according to the present embodiment has excellent electrical characteristics. The benzoquinone methide derivative (1) is represented by the general formula (1).
[ CHEM 4 ]
In the general formula (1), R1Represents: general formula (2), C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl, nitro, C2-C7 alkoxycarbonyl or halogen atom. R1The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R1The C6-C14 aryl group may have a first substituent. R2And R3Independently of each other, represents: C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl or halogen atom. R2And R3The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R2And R3The C6-C14 aryl group shown may also have a second substituent. m represents an integer of 0 to 5 inclusive. When m represents an integer of 2 to 5 inclusive, a plurality of R1May be the same or different from each other.
[ CHEM 5 ]
In the general formula (2), R4And R5Independently of each other, represents: C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl or halogen atom. R4And R5The C1-C6 alkyl groups represented may also have C6-C14 aryl groups. R4And R5The C6-C14 aryl group may have a third substituent. The first substituent, the second substituent and the third substituent are each independently represented by: C1-C6 alkyl, C1-C6 alkoxy, C6-C14 aryl, C1-C7 acyl or halogen atom. The C1-C6 alkyl group represented by the first substituent, the second substituent and the third substituent may also have a C6-C14 aryl group.
The benzoquinone methide derivative (1) will be described in detail below. In the general formula (1), R1The halogen atom represented is preferably a chlorine atom. R1The C2-C7 alkoxycarbonyl group is preferably a C2-C4 alkoxycarbonyl group, more preferably a methoxycarbonyl group.
In the general formula (1), R1Preferably represents a halogen atom, a nitro group or a C2-C7 alkoxy group of the formula (2)The carbonyl group is more preferably a chlorine atom, a nitro group or a C2-C4 alkoxycarbonyl group.
In the general formula (1), R is based on the bonding position of the ester group on the benzene ring1Substitution may be made in the ortho (o position), meta (m position) or para (p position). Among them, ortho-or para-position is preferable. m preferably represents 1 or 2.
In the general formula (1), R2And R3The C1-C6 alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl group or a tert-butyl group.
In the general formula (2), R4And R5The C1-C6 alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl group or a tert-butyl group.
In the general formula (1), preferred is: r1Represents a halogen atom, a nitro group or a C2-C7 alkoxycarbonyl group, R2And R3R in the general formula (2) represents a C1-C4 alkyl group4And R5Represents a C1-C4 alkyl group.
The benzoquinone methide derivative (1) may have 1 or 2 benzoquinone methylated moieties. In the case where the benzoquinone methide derivative (1) has 1 benzoquinone methylated moiety, in the general formula (1), it is preferable that: r1Represents a halogen atom, a nitro group or a C2-C7 alkoxycarbonyl group, R2And R3Represents a C1-C4 alkyl group, and m represents 1 or 2. In the case where m represents 2, 2R1Preferably different from each other.
In the case where the benzoquinone methide derivative (1) has 2 benzoquinone methylated moieties, in the general formula (1), it is preferable that: r1Represents a general formula (2), R2And R3Represents a C1-C4 alkyl group, m represents 1, and R in the general formula (2)4And R5Represents a C1-C4 alkyl group.
Specific examples of the benzoquinone methide derivative (1) include: benzoquinone methide derivatives represented by chemical formulas (1-1) to (1-5) (hereinafter, sometimes referred to as benzoquinone methide derivatives (1-1) to (1-5), respectively).
[ CHEM 6 ]
[ CHEM 7 ]
[ CHEM 8 ]
[ CHEM 9 ]
[ CHEM 10 ]
Among these benzoquinone methide derivatives (1), benzoquinone methide derivatives (1-1) and (1-4) are preferable from the viewpoint of improving the sensitivity characteristics of the photoreceptor.
When the photoreceptor is a multilayer photoreceptor, the content of the benzoquinone methide derivative (1) is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 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.
When the photoreceptor is a single-layer photoreceptor, the content of the benzoquinone methide derivative (1) is preferably 10 to 200 parts by mass, more preferably 10 to 100 parts by mass, and particularly preferably 10 to 75 parts by mass, based on 100 parts by mass of the binder resin contained in the single-layer photosensitive layer.
The charge transport layer may contain other electron acceptor compounds in addition to the benzoquinone methide derivative (1). The monolayer photosensitive layer may contain an electron-transporting agent other than the benzoquinone methide derivative (1). Other electron acceptor compounds and electron transporters are, for example: quinone compounds, imide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3, 4, 5, 7-tetranitro-9-fluorenone compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2, 4, 8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride or dibromomaleic anhydride. Examples of the quinone compound include: a diphenoquinone compound, an azoquinone compound, an anthraquinone compound, a naphthoquinone compound, a nitroanthraquinone compound or a dinitroanthraquinone compound. One of these electron transport agents and electron acceptor compounds may be used alone, or two or more of these may be used in combination.
(Process for producing benzoquinone methide derivative (1))
For example, the benzoquinone methide derivative (1) can be produced by a reaction represented by the reaction equation (R-1) (hereinafter, sometimes referred to as reaction (R-1)) and a reaction represented by the reaction equation (R-2) (hereinafter, sometimes referred to as reaction (R-2)), or by a similar method. The process for producing the benzoquinone methide derivative (1) comprises, for example, the reaction (R-1) and the reaction (R-2).
In the reaction (R-1), R in the general formula (A) and the general formula (C)2And R3Are respectively connected with R in the general formula (1)2And R3The meaning is the same. R in the general formula (B) and the general formula (C)1And m is independently from R in the formula (1)1And m have the same meaning.
[ CHEM 11 ]
In the reaction (R-1), 1 equivalent of the alcohol derivative represented by the general formula (a) (hereinafter, sometimes referred to as the alcohol derivative (a)) and 1 equivalent of the carboxylic acid derivative represented by the general formula (B) (hereinafter, sometimes referred to as the carboxylic acid derivative (B)) are reacted in a solvent in the presence of a dehydration condensation agent and a catalyst to obtain 1 equivalent of the ester derivative represented by the general formula (C) (hereinafter, sometimes referred to as the ester derivative (C)). In the reaction (R-1), a dehydration condensation agent is preferably added in an amount of 1 to 5 moles based on 1 mole of the alcohol derivative (a). When the dehydration condensation agent is added in an amount of 1 to 5 moles based on 1 mole of the alcohol derivative (a), the yield of the benzoquinone methide derivative (1) can be easily increased, and the purification of the benzoquinone methide derivative (1) can be easily performed. When the catalyst is added in an amount of 0.1 to 0.5 mol based on 1 mol of the alcohol derivative (a), the yield of the benzoquinone methide derivative (1) can be easily increased, and the benzoquinone methide derivative (1) can be easily purified. The reaction time of the reaction (R-1) is preferably 3 hours or more and 15 hours or less. The reaction temperature of the reaction (R-1) is preferably 0 ℃ to 50 ℃. Examples of the solvent include: chloroform or dichloromethane. Examples of the dehydration condensation agent include: dicyclohexylcarbodiimide or carbonyldiimidazole. Examples of the catalyst include: dimethylaminopyridine or triethylamine.
In the reaction (R-2), R in the general formula (C)1、R2、R3And m is independently from R in the formula (1)1、R2、R3And m have the same meaning.
[ CHEM 12 ]
In the reaction (R-2), 1 equivalent of the ester derivative (C) is reacted in a solvent in the presence of an oxidizing agent to obtain 1 equivalent of the benzoquinone methide derivative (1). In the reaction (R-2), it is preferable to add 1 to 10 moles of the oxidizing agent to 1 mole of the ester derivative (C). When the oxidizing agent is added in an amount of 1 to 10 moles based on 1 mole of the ester derivative (C), the yield of the benzoquinone methide derivative (1) can be easily increased, and the benzoquinone methide derivative (1) can be easily purified. The reaction time of the reaction (R-2) is preferably 3 hours or more and 15 hours or less. The reaction temperature of the reaction (R-1) is preferably 0 ℃ to 50 ℃. Examples of the solvent include: chloroform or dichloromethane. Examples of the oxidizing agent include: potassium permanganate, hydrogen peroxide, m-chloroperoxybenzoic acid, or peracetic acid.
The process for producing the benzoquinone methide derivative (1) may optionally include other steps (e.g., purification step). Such a step includes, for example, a purification step. The purification method may be, for example, a known method (more specifically, filtration, chromatography, crystallization, or the like).
<5. hole-transporting agent >
For example, a nitrogen-containing cyclic compound or a condensed polycyclic compound can be used as the hole transporting agent. Examples of the nitrogen-containing cyclic compound and the condensed polycyclic compound include: diamine derivatives (more specifically, N ' -tetraphenylphenylenediamine derivatives, N ' -tetraphenylbenzidine derivatives, N ' -tetraphenylnaphthalenediamine derivatives, or N, N ' -tetraphenylphenylenediamine (N, N ' -tetraphenylphenylenediamine) derivatives, etc.), oxadiazole compounds (more specifically, 2, 5-bis (4-methylaminophenyl) -1, 3, 4-oxadiazole, etc.), styrene compounds (more specifically, 9- (4-diethylaminostyryl) anthracene, etc.), carbazole compounds (more specifically, polyvinylcarbazole, etc.), organic polysilane compounds, pyrazoline compounds (more specifically, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, etc.), hydrazone compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds or triazole compounds. One of these hole transport agents may be used alone, or two or more of them may be used in combination. Among these hole transport agents, compounds represented by the general formula (3) (benzidine derivatives) are preferable.
[ CHEM 13 ]
In the general formula (3), R21、R22、R23、R24、R25And R26Independently of one another, represents a C1-C6 alkyl group or a C1-C6 alkoxy group. r, s, v and w are each independently an integer of 0 to 5. t and u are each independently an integer of 0 to 4.
In the general formula (3), R21、R22、R23、R24、R25And R26Each independently preferably represents a C1-C6 alkyl group, more preferably a C1-C3 alkyl group, and still more preferably a methyl group. r, s, v, w, t and u preferably represent 1.
The compound represented by the general formula (3) is preferably a compound represented by the chemical formula (H-1) (hereinafter, may be referred to as a hole transporting agent (H-1)).
[ CHEM 14 ]
When the photoreceptor is a multilayer photoreceptor, the content of the hole transporting agent is preferably 10 parts by mass or more and 200 parts by mass or less, and more preferably 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 transporting layer.
When the photoreceptor is a single-layer photoreceptor, the content of the hole transporting agent is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, and particularly preferably 10 parts by mass or more and 90 parts by mass or less, with respect to 100 parts by mass of the binder resin contained in the single-layer photosensitive layer.
<6. Charge generating agent >
The charge generating agent is not particularly limited as long as it is a charge generating agent for a photoreceptor. Examples of the charge generating agent include: phthalocyanine pigments, perylene pigments, disazo pigments, trisazo pigments, dithione-pyrrolopyrrole (dithioketo-pyrrozole) pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaric acid pigments, indigo pigments, azulene pigments, cyanine pigments, powders of inorganic photoconductive materials (more specifically, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, or the like), pyran pigments, anthanthroquinone pigments, triphenylmethane pigments, threne pigments, toluidine pigments, pyrazoline pigments, or quinacridone pigments. One kind of charge generating agent may be used alone, or two or more kinds may be used in combination.
Examples of the phthalocyanine pigments include: a metal-free phthalocyanine represented by the formula (C-1) (hereinafter, may be referred to as a charge generator (C-1)) or a metal phthalocyanine. Examples of the metal phthalocyanine include: oxytitanium phthalocyanine (hereinafter, sometimes referred to as a charge generator (C-2)), hydroxygallium phthalocyanine or chlorogallium phthalocyanine represented by the chemical formula (C-2). The phthalocyanine pigment may be crystalline or amorphous. The crystal shape (for example, α -type, β -type, Y-type, V-type, or II-type) of the phthalocyanine pigment is not particularly limited, and phthalocyanine pigments having various crystal shapes can be used.
[ CHEM 15 ]
[ CHEM 16 ]
Examples of the metal-free phthalocyanine include: an X-type crystal of metal-free phthalocyanine (hereinafter, sometimes referred to as X-type metal-free phthalocyanine). Examples of the crystal of oxytitanium phthalocyanine include: an α -type, β -type or Y-type crystal of oxytitanium phthalocyanine (hereinafter, sometimes referred to as α -type, β -type or Y-type oxytitanium phthalocyanine). Examples of the crystals of hydroxygallium phthalocyanine include: crystals of hydroxygallium phthalocyanine in form V. Examples of the crystal of chlorogallium phthalocyanine include: type II crystal of chlorogallium phthalocyanine.
For example, in a digital optical image forming apparatus, it is preferable to use a photoreceptor having sensitivity in a wavelength region of 700nm or more. Examples of such an image forming apparatus include: a laser printer or a facsimile machine having a semiconductor laser. Phthalocyanine-based pigments are preferable as the charge generating agent, and metal-free phthalocyanines or oxytitanium phthalocyanines are more preferable as the charge generating agent, because of high quantum yield in the wavelength region of 700nm or more. When the photosensitive layer contains the benzoquinone methide derivative (1), X-type metal-free phthalocyanine or Y-type oxytitanium phthalocyanine is more preferable as the charge generating agent in order to further improve the electrical characteristics of the photoreceptor.
The Y-type oxytitanium phthalocyanine has a main peak at 27.2 ° of the bragg angle (2 θ ± 0.2 °) in the CuK α characteristic X-ray diffraction spectrum, for example. The main peak in the CuK α characteristic X-ray diffraction spectrum means a peak having a first or second large intensity in a range where the bragg angle (2 θ ± 0.2 °) is 3 ° or more and 40 ° or less.
(method for measuring CuK alpha characteristic X-ray diffraction Spectrum)
An example of a method for measuring a characteristic X-ray diffraction spectrum of CuK α will be described, in which a sample (oxytitanium phthalocyanine) is filled in a sample holder of an X-ray diffraction apparatus (for example, "RINT (registered trademark in Japan) 1100" manufactured by Rigaku Corporation), and the X-ray diffraction spectrum is measured under measurement conditions of an X-ray tube Cu, a tube voltage of 40kV, a tube current of 30mA, and a wavelength of CuK α characteristic X-rays
The measurement range (2 θ) is 3 ° to 40 ° (start angle 3 ° and stop angle 40 °), and the scanning speed is 10 °/min.
In the photoreceptor used in the image forming apparatus using the short-wavelength laser light source, an anthraquinone-based pigment is preferably used as the charge generating agent. The wavelength of the short-wavelength laser light is, for example, 350nm to 550 nm.
When the photoreceptor is a laminated photoreceptor, the content of the charge generating agent is preferably 5 parts by mass or more and 1000 parts by mass or less, and more preferably 30 parts by mass or more and 500 parts by mass or less, with respect to 100 parts by mass of the matrix resin contained in the charge generating layer.
When the photoreceptor is a single-layer photoreceptor, the content of the charge generating agent is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and particularly preferably 0.5 to 6.0 parts by mass, based on 100 parts by mass of the binder resin contained in the single-layer photosensitive layer.
<7. Binder resin >
Examples of the binder resin include: a thermoplastic resin, a thermosetting resin, or a photocurable resin. Examples of the thermoplastic resin include: a polycarbonate resin, a polyarylate resin, a styrene-butadiene resin, a styrene-acrylonitrile resin, a styrene-maleic acid resin, an acrylic resin, a styrene-acrylic resin, a polyethylene resin, an ethylene-vinyl acetate resin, a chlorinated polyethylene resin, a polyvinyl chloride resin, a polypropylene resin, an ionomer resin, a vinyl chloride-vinyl acetate resin, an alkyd resin, a polyamide resin, a polyurethane resin, a polysulfone resin, a diallyl phthalate resin, a ketone resin, a polyvinyl butyral resin, a polyester resin, or a polyether resin. Examples of the thermosetting resin include: silicone resin, epoxy resin, phenol resin, urea resin, or melamine resin. Examples of the photocurable resin include: an epoxy-acrylic resin (more specifically, an acrylic acid derivative adduct of an epoxy compound, etc.) or a urethane-acrylic resin (more specifically, an acrylic acid derivative adduct of a urethane compound, etc.). These binder resins may be used alone or in combination of two or more.
Among these resins, polycarbonate resins are preferred from the viewpoint of obtaining a monolayer type photosensitive layer and a charge transport layer which are excellent in balance among processability, mechanical strength, optical performance and abrasion resistance. Examples of the polycarbonate resin include: a bisphenol Z-type polycarbonate Resin having a repeating unit represented by the following chemical formula (Resin-1) (hereinafter, may be referred to as a polycarbonate Resin (Resin-1)).
[ CHEM 17 ]
The viscosity average molecular weight of the binder resin is preferably 40,000 or more, and more preferably 40,000 or more and 52,500 or less. When the viscosity average molecular weight of the binder resin is 40,000 or more, the abrasion resistance of the photoreceptor is easily improved. When the viscosity average molecular weight of the binder resin is 52,500 or less, the binder resin is easily dissolved in a solvent at the time of forming the photosensitive layer, and the viscosity of the coating liquid for the charge transport layer or the coating liquid for the single-layer photosensitive layer is not excessively high. As a result, the charge transport layer or the monolayer type photosensitive layer is easily formed.
<8. base resin >
When the photoreceptor is a laminated photoreceptor, the charge generation layer may contain a matrix resin. The base resin is not particularly limited as long as it is a base resin that can be used in a photoreceptor. Examples of the matrix resin include: a thermoplastic resin, a thermosetting resin, or a photocurable resin. Examples of the thermoplastic resin include: styrene-butadiene resin, styrene-acrylonitrile resin, styrene-maleic acid resin, styrene-acrylic resin, polyethylene resin, ethylene-vinyl acetate resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate resin, alkyd resin, polyamide resin, polyurethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, or polyester resin. Examples of the thermosetting resin include: silicone resins, epoxy resins, phenolic resins, urea-formaldehyde resins, melamine resins, or other cross-linking thermosetting resins. Examples of the photocurable resin include: an epoxy-acrylic resin (more specifically, an acrylic acid derivative adduct of an epoxy compound, etc.) or a urethane-acrylic resin (more specifically, an acrylic acid derivative adduct of a urethane compound, etc.). The base resin may be used alone or in combination of two or more.
The matrix resin contained in the charge generating layer is preferably different from the binder resin contained in the charge transporting layer. The reason is to insolubilize the charge generation layer in the solvent of the coating liquid for charge transport layer. In the production of a laminated photoreceptor, it is common to form a charge generation layer on a conductive substrate and a charge transport layer on the charge generation layer, and in the formation of the charge transport layer, a charge transport layer coating solution is applied to the charge generation layer.
<9. additive >
The photosensitive layer (charge generation layer, charge transport layer, or single layer photosensitive layer) of the photoreceptor may contain various additives as necessary. Examples of additives include: a deterioration inhibitor (more specifically, an antioxidant, a radical scavenger, a quencher or an ultraviolet absorber, etc.), a softening agent, a surface modifier, an extender, a thickener, a dispersion stabilizer, a wax, a donor, a surfactant, a plasticizer, a sensitizer or a leveling agent. Examples of the antioxidant include: hindered phenols (more specifically, di-t-butyl-p-cresol and the like), hindered amines, p-phenylenediamine, arylalkanes, hydroquinones, spirochromans (spirochromans), spiroindanones (spiroindanones) or derivatives thereof; organic sulfur compounds or organic phosphorus compounds.
<10. intermediate layer >
The intermediate layer (undercoat layer) contains, for example, inorganic particles and a resin (resin for intermediate layer). It can be considered that: the presence of the intermediate layer allows smooth current flow to be generated when the photoreceptor is exposed, while maintaining an insulating state to such an extent that leakage current can be suppressed, thereby suppressing an increase in resistance.
Examples of the inorganic particles include: particles of a metal (more specifically, aluminum, iron, copper, or the like), particles of a metal oxide (more specifically, titanium oxide, aluminum oxide, zirconium oxide, tin oxide, zinc oxide, or the like), or particles of a non-metal oxide (more specifically, silicon dioxide, or the like). These inorganic particles may be used alone or in combination of two or more.
The resin for the intermediate layer is not particularly limited as long as it is a resin that can be used to form the intermediate layer. The intermediate layer may also contain various additives. The additives are the same as those of the photosensitive layer.
<11 > method for producing photoreceptor
When the photoreceptor is a laminated photoreceptor, the laminated photoreceptor is produced, for example, as follows. First, a coating liquid for a charge generating layer and a coating liquid for a charge transporting layer are prepared. The coating liquid for the charge generation layer is applied to the conductive substrate to form a coating film. The coating film is dried, thereby forming a charge generation layer. Next, a coating liquid for a charge transport layer is coated on the charge generation layer to form a coating film. The coating film is dried, thereby forming a charge transport layer. Thus, a laminated photoreceptor was produced.
The coating liquid for the charge generating layer contains, for example: a charge generating agent, a matrix resin, a solvent, and an additive. For example, the coating liquid for a charge generating layer is prepared by dissolving or dispersing a charge generating agent, a matrix resin, and an additive in a solvent. The coating liquid for a charge transport layer contains, for example: a hole-transporting agent, a benzoquinone methide derivative (1) as an electron acceptor compound, a binder resin, and an additive. For example, the coating liquid for a charge transport layer is prepared by dissolving or dispersing the hole transport agent, the benzoquinone methide derivative (1) as the electron acceptor compound, the binder resin, and the additive in a solvent.
Next, in the case where the photoreceptor is a single-layer photoreceptor, for example, a single-layer photoreceptor is produced by coating a conductive substrate with a coating solution for a single-layer photosensitive layer to form a coating film and drying the coating film. The coating liquid for the monolayer photosensitive layer contains, for example: a charge generating agent, a hole transporting agent, a benzoquinone methide derivative (1) as an electron transporting agent, a binder resin, and an additive. For example, a charge generator, a hole transport agent, a benzoquinone methide derivative (1) as an electron transport agent, a binder resin, and an additive are dissolved or dispersed in a solvent to prepare a coating liquid for a monolayer photosensitive layer.
The solvent contained in the coating liquid for the charge generating layer, the coating liquid for the charge transporting layer, or the coating liquid for the single-layer photosensitive layer (hereinafter, these coating liquids may be referred to as coating liquids) is not particularly limited as long as it can dissolve or disperse the respective components contained in the coating liquid. Examples of the solvent include: alcohols (more specifically, methanol, ethanol, isopropanol, butanol, or the like), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, or the like), aromatic hydrocarbons (more specifically, benzene, toluene, xylene, or the like), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, or the like), ethers (more specifically, dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, or the like), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, or the like), esters (more specifically, ethyl acetate, methyl acetate, or the like), dimethyl formaldehyde, dimethyl formamide, or dimethyl sulfoxide. These solvents may be used alone or in combination of two or more. In order to improve the workability in manufacturing the photoreceptor, a non-halogenated solvent (a solvent other than halogenated hydrocarbon) is preferably used as the solvent.
A coating liquid was prepared by mixing and dispersing the respective components into a solvent. For the mixing or dispersing operation, for example, a bead mill, a roll mill, a ball mill, an attritor, a paint shaker or an ultrasonic disperser can be used.
For example, the coating liquid may contain a surfactant in order to improve dispersibility of each component.
The method of coating with the coating liquid is not particularly limited as long as the coating liquid can be uniformly applied to the conductive substrate. Examples of the coating method include: dip coating, spray coating, spin coating or bar coating.
The method for drying the coating liquid is not particularly limited as long as it can remove at least a part of the solvent in the coating liquid. For example, a method of performing heat treatment (hot air drying) using a high-temperature dryer or a reduced-pressure dryer is given as the removal method. For example, the heat treatment conditions are preferably 40 ℃ to 150 ℃ and 3 minutes to 120 minutes.
The method for producing the 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, a known method is appropriately selected.
The photoreceptor according to the present embodiment is explained above. The photoreceptor according to the present embodiment has excellent electrical characteristics.
[ examples ] A method for producing a compound
The present invention will be described in more detail with reference to examples. However, the present invention is not limited in any way to the scope of the examples.
<1. materials for photoreceptors >
The following hole transporting agent, charge generating agent and electron transporting agent were prepared as materials for forming the single-layer photosensitive layer of the single-layer photoreceptor.
<1-1. Electron transport agent >
The following methods were used to produce the quinone methide derivatives (1-1) to (1-5) as the electron transport agents, respectively.
<1-1-1 > production of benzoquinone methide derivative (1-1) >
The benzoquinone methide derivative (1-1) is produced according to the reaction (r-1) and the reaction (r-2).
[ CHEM 18 ]
In the reaction (r-1), an alcohol derivative represented by the chemical formula (A-1) (hereinafter, sometimes referred to as an alcohol derivative (A-1)) and a carboxylic acid derivative represented by the chemical formula (B-1) (hereinafter, sometimes referred to as a carboxylic acid derivative (B-1)) are reacted to obtain an ester derivative represented by the chemical formula (C-1) (hereinafter, sometimes referred to as an ester derivative (C-1)). Specifically, 2.36g (10mmol) of the alcohol derivative (A-1), 2.02g (10mmol) of the carboxylic acid derivative (B-1), 0.18g (1.5mmol) of dimethylaminopyridine as a catalyst, and chloroform were placed in a reaction vessel to prepare a chloroform solution. 3.2g (15mmol) of dicyclohexylcarbodiimide as a dehydration-condensation agent was added dropwise to the reaction vessel, and the contents of the reaction vessel were stirred at room temperature (25 ℃ C.) for 8 hours. The contents of the reaction vessel were then filtered to obtain a filtrate. The solvent of the obtained filtrate was evaporated to obtain a residue. The obtained residue was purified by silica gel column chromatography using chloroform as a developing solvent. As a result, an ester derivative (C-1) was obtained. In the reaction (r-1), the yield of the ester derivative (C-1) was 2.7g based on the alcohol derivative (A-1), and the yield of the ester derivative (C-1) was 64 mol%.
[ CHEM 19 ]
In the reaction (r-2), 2.1g (5mmol) of the ester derivative (C-1) and chloroform were placed in a reaction vessel to prepare a chloroform solution. Further, 3.9g (25mmol) of potassium permanganate as an oxidizing agent was put into the reaction vessel, and the contents of the reaction vessel were stirred at room temperature (25 ℃) for 8 hours. The contents of the reaction vessel were then filtered to obtain a filtrate. The solvent of the obtained filtrate was evaporated to obtain a residue. The obtained residue was purified by silica gel column chromatography using chloroform as a developing solvent. As a result, the quinone methide derivative (1-1) was obtained. In the reaction (r-2), the yield of the benzoquinone methide derivative (1-1) was 1.25g and the yield of the benzoquinone methide derivative (1-1) was 60 mol%, based on the ester derivative (C-1).
<1-1-2 > production of benzoquinone methide derivatives (1-2) to (1-5) >
The benzoquinone methide derivatives (1-2) to (1-5) were produced by the same method as the production of the benzoquinone methide derivative (1-1) except that the following points were changed.
In Table 1, the alcohol derivative (A), the carboxylic acid derivative (B) and the ester derivative (C) in the reaction (r-1) are shown. Wherein the alcohol derivative (A) and the carboxylic acid derivative (B) are reactants (Reactant) in the reaction (r-1). The alcohol derivative (A-1) and the carboxylic acid derivative (B-1) used in the reaction (r-1) were changed to the alcohol derivative (A) and the carboxylic acid derivative (B) shown in Table 1, respectively. As a result, ester derivatives (C-2) to (C-5) were obtained in place of the ester derivative (C-1). In table 1, the yield and yield of the ester derivative (C) are shown.
In Table 1, A-1 and A-2 in the column "type" of alcohol derivative (A) represent alcohol derivatives (A-1) and (A-2), respectively. In the column "type" of carboxylic acid derivative (B), B-1, B-2, B-3, B-4 and B-5 respectively represent alcohol derivatives (B-1), (B-2), (B-3), (B-4) and (B-5). C-1, C-2, C-3, C-4 and C-5 in the column "category" of the ester derivative (C) represent ester derivatives (C-1), (C-2), (C-3), (C-4) and (C-5), respectively.
[ TABLE 1 ]
The alcohol derivative (A-2) is represented by the following chemical formula (A-2). The carboxylic acid derivatives (B-2) to (B-5) are represented by the following chemical formulae (B-2) to (B-5), respectively. The ester derivatives (C-2) to (C-5) are represented by the following chemical formulae (C-2) to (C-5), respectively.
[ CHEM 20 ]
[ CHEM 21 ]
[ CHEM 22 ]
[ CHEM 23 ]
[ CHEM 24 ]
[ CHEM 25 ]
[ CHEM 26 ]
[ CHEM 27 ]
[ CHEM 28 ]
In Table 2, the ester derivative (C) and the benzoquinone methide derivative (1) in the reaction (r-2) are shown. Wherein the ester derivative (C) is a Reactant (Reactant) in the reaction (r-2). The ester derivative (C-1) used in the reaction (r-2) was changed to the ester derivative (C) shown in Table 2. As a result, the quinone methide derivatives (1-2) to (1-5) were obtained in place of the quinone methide derivative (1-1). In Table 2, the yields and yields of the benzoquinone methide derivative (1) are shown.
In Table 2, C-1, C-2, C-3, C-4 and C-5 in the column "kind" of the ester derivative (C) represent ester derivatives (C-1), (C-2), (C-3), (C-4) and (C-5), respectively. 1-1, 1-2, 1-3, 1-4 and 1-5 in the column "category" of the benzoquinone methide derivatives (1) represent the benzoquinone methide derivatives (1-1), (1-2), (1-3), (1-4) and (1-5), respectively.
[ TABLE 2 ]
Next, the infrared absorption spectra of the prepared quinone methide derivatives (1-1) to (1-5) were measured using a Fourier transform infrared spectrophotometer ("SPECTRUMONE" manufactured by Perkinelmer corporation). The preparation of the samples was carried out by KBr (potassium bromide) tabletting. The quinone methide derivatives (1-1) to (1-5) were confirmed to be obtained from the measured infrared absorption spectra, respectively. Of these, benzoquinone methide derivatives (1-1) and (1-4) are typical examples.
FIGS. 3 to 4 show the infrared absorption spectra of the quinone methide derivatives (1-1) and (1-4), respectively. In FIGS. 3 to 4, the vertical axis represents transmittance (%) and the horizontal axis represents wave number (unit: cm)-1). The unit% of the vertical axis (transmittance) in fig. 3 to 4 is an arbitrary unit. The wave number (vMAX) of the absorption peak of the infrared absorption spectrum is shown below.
Benzoquinone methide derivative (1-1): IR cm-1：2967，1720，1655，1317，1244，1154，921，879.
Benzoquinone methide derivatives (1-4): IR cm-1：2963，1725，1657，1280，1109，755.
<1-1-4. preparation of Compound (E-1), Compound (E-2) and Compound (E-3) >
Compounds represented by the chemical formulas (E-1), (E-2) and (E-3) (hereinafter, sometimes referred to as compounds (E-1), (E-2) and (E-3), respectively)) were prepared as electron-transporting agents.
[ CHEM 29 ]
[ CHEM 30 ]
[ CHEM 31 ]
<1-2. hole transporting agent >
The hole-transporting agent (H-1) described above was prepared.
<1-3. Charge generating agent >
The charge generators (C-1) to (C-2) described above were prepared. The charge generating agent (C-1) is a metal-free phthalocyanine (X-type metal-free phthalocyanine) represented by the formula (C-1). The crystal structure of the charge generating agent (C-1) is X-type.
The charge generating agent (C-2) is oxytitanium phthalocyanine (Y-type oxytitanium phthalocyanine) represented by the formula (C-2). The crystal structure of the charge generating agent (C-2) is Y-type. In the X-ray diffraction spectrum of Y-type oxytitanium phthalocyanine, it was confirmed that the crystal had a main peak at a bragg angle (2 θ ± 0.2 °) of 27.2 °.
<1-4. Binder resin >
A polycarbonate Resin (Resin-1) described in the first embodiment (manufactured by Diko corporation "PANLITE (Japanese registered trademark) TS-2050"; viscosity-average molecular weight: 50,000) was prepared as a binder Resin.
<2 > production of Single-layer photoreceptor
Single-layer photoreceptors (A-1) to (A-10) and single-layer photoreceptors (B-1) to (B-6) were produced using a material for forming a photosensitive layer.
<2-1 > production of Single-layer photoreceptor (A-1) >
5 parts by mass of a charge generating agent (C-1), 80 parts by mass of a hole transporting agent (H-1), 40 parts by mass of a benzoquinone methide derivative (1-1) as an electron transporting agent, 100 parts by mass of a polycarbonate Resin (Resin-1) as a binder Resin, and 800 parts by mass of tetrahydrofuran as a solvent were charged in a vessel. These materials (charge generating agent (C-1), hole transporting agent (H-1), benzoquinone methide derivative (1-1) and polycarbonate Resin (Resin-1)) were mixed with a solvent for 50 hours using a ball mill, and the materials were dispersed in the solvent. Thus, a coating liquid for a monolayer photosensitive layer was obtained. A coating liquid for a monolayer type photosensitive layer was applied to an aluminum drum-shaped support (diameter: 30mm, total length: 238.5mm) as a conductive substrate by a dip coating method to form a coating film. The coated film was dried with hot air at 100 ℃ for 30 minutes. Thus, a monolayer type photosensitive layer (film thickness: 30 μm) was formed on the conductive substrate. As a result, the single-layer photoreceptor (A-1) was obtained.
<2-2 > production of Single-layer photoreceptors (A-2) to (A-10) and Single-layer photoreceptors (B-1) to (B-6) >
The single-layer photoreceptors (A-2) to (A-10) and the single-layer photoreceptors (B-1) to (B-6) were produced by the same method as the production of the single-layer photoreceptor (A-1) except for the following points. The charge generating agent (C-1) used for the production of the single layer type photoreceptor (A-1) was changed to the one shown in Table 3. The quinone methide derivative (1-1) as the electron transporting agent used for producing the single layer type photoreceptor (A-1) was changed to the electron transporting agent of the type shown in Table 3. In addition, in Table 3, the structures of the photoreceptors (A-1) to (A-10) and the photoreceptors (B-1) to (B-6) are shown. In table 3, CGM, HTM, and ETM represent a charge generating agent, a hole transporting agent, and an electron transporting agent, respectively. In Table 3, column "CGM" x-H2Pc and Y-TiOPc represent X-type metal-free phthalocyanine (charge generating agent (C-1)) and Y-type oxytitanium phthalocyanine (charge generating agent (C-2)), respectively. In column "HTMH-1 of (A) represents a hole transporting agent (H-1). In the column "ETM", 1-1 to 1-5 and E-1 to E-3 represent benzoquinone methide derivatives (1-1) to (1-5) and compounds (E-1) to (E-3), respectively.
<3. evaluation of photoreceptor Properties >
<3-1. evaluation of sensitivity characteristics of Single layer type photoreceptor >
The manufactured single-layer photoreceptors (A-1) to (A-10) and the single-layer photoreceptors (B-1) to (B-6) were evaluated for sensitivity characteristics. The sensitivity characteristic evaluation was performed under an environment of 23 ℃ temperature and 60% RH humidity. First, the surface of the single layer type photoreceptor is charged to a positive polarity using a drum sensitivity tester (manufactured by GENTEC corporation). The charging conditions were set to a rotation speed of 31rpm of the single-layer type photoreceptor and a current flowing into the single-layer type photoreceptor of +8 μ a. The surface potential of the single-layer photoreceptor immediately after charging was set to + 700V. Then, monochromatic light (wavelength of 780nm, half-width of 20nm, light energy of 1.5. mu.J/cm) was extracted from the white light of the halogen lamp using a band-pass filter2). The extracted monochromatic light is irradiated onto the surface of the single-layer type photoreceptor. The surface potential of the single layer type photoreceptor after 0.5 second from the end of the irradiation was measured. The measured surface potential was recorded as the sensitometric potential (V)LUnit V). Measured sensitivity potential (V) of single-layer type photoreceptorL) Shown in table 3. In addition, light sensitivity potential (V)L) The smaller the absolute value of (a) is, the more excellent the electrical characteristics of the single layer type photoreceptor are.
[ TABLE 3 ]
As shown in Table 3, in the photoreceptors (A-1) to (A-10), the photosensitive layer contained one of the benzoquinone methide derivatives (1-1) to (1-5) as an electron transporting agent. These quinone methide derivatives (1-1) to (1-5) are all compounds represented by the general formula (1). In addition, in the photoreceptors (A-1) to (A-10), the sensitivity potential VLIs +107V or more and +116V or less.
As shown in Table 3, the photoreceptors (B-1) to (B-6) each had a photosensitive layerThe compound (E-1), (E-2) or (E-3) is used as an electron transporting agent. The compounds (E-1), (E-2) and (E-3) are not compounds represented by the general formula (1). In addition, in the photoreceptors (B-1) to (B-6), the sensitivity potential V was set toLIs not less than +119V and not more than + 130V.
The photoreceptors (A-1) to (A-10) containing the benzoquinone methide derivatives (1-1) to (1-5) are clearly superior in sensitivity characteristics to the photoreceptors (B-1) to (B-6) containing the compounds (E-1) to (E-3).
From the above, it is apparent that when the benzoquinone methide derivative represented by the general formula (1) is contained in the photosensitive layer of the photoreceptor, the photoreceptor is excellent in sensitivity characteristics.
Claims (6)
1. An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer,
the photosensitive layer contains a charge generator, a hole transporting agent, a benzoquinone methide derivative and a binder resin,
the benzoquinone methide derivative is represented by chemical formula (1-1), chemical formula (1-2) or chemical formula (1-3),
2. the electrophotographic photoreceptor according to claim 1,
the hole-transporting agent contains a compound represented by the general formula (3),
in the general formula (3) described above,
R21、R22、R23、R24、R25and R26Independently of one another, represents C1-C6 alkyl or C1-C6 alkoxy,
r, s, v and w are each independently an integer of 0 to 5,
t and u are each independently an integer of 0 to 4.
3. The electrophotographic photoreceptor according to claim 2,
in the general formula (3) described above,
R21、R22、R23、R24、R25and R26Independently of one another, represents a C1-C6 alkyl group,
r, s, v, w, t and u represent 1.
4. The electrophotographic photoreceptor according to claim 2,
the hole transporting agent is represented by the formula (H-1),
5. the electrophotographic photoreceptor according to claim 1 or 2,
the charge generating agent contains X-type metal-free phthalocyanine or Y-type oxytitanium phthalocyanine.
6. The electrophotographic photoreceptor according to claim 1 or 2,
the photosensitive layer is a monolayer type photosensitive layer.
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| CN101371201A (en) * | 2006-01-18 | 2009-02-18 | 富士电机电子技术株式会社 | Quinone compound, electrophotographic photosensitive body and electrophotographic apparatus |
| CN103415498A (en) * | 2010-12-06 | 2013-11-27 | 赛泽恩有限公司 | Benzylidene substituted 2,4-pentanedione compounds and use thereof as stabilizers |
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| KR100462626B1 (en) * | 2002-11-18 | 2004-12-23 | 삼성전자주식회사 | Polymer having stilbenequinone structure and electrophotographic photoreceptor comprising the same |
| JP5865307B2 (en) * | 2013-07-31 | 2016-02-17 | 京セラドキュメントソリューションズ株式会社 | Electrophotographic photosensitive member and image forming apparatus |
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| CN103415498A (en) * | 2010-12-06 | 2013-11-27 | 赛泽恩有限公司 | Benzylidene substituted 2,4-pentanedione compounds and use thereof as stabilizers |
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