JP2003295484A - Monolayer organic photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monolayer organic photoreceptor in which wear of a photosensitive layer is effectively suppressed, tendency for deterioration in electrophotographic characteristics such as sensitivity by wear of the photosensitive layer is tempered, and durability is significantly improved. <P>SOLUTION: In the monolayer organic photoreceptor having a monodispersion type photosensitive layer containing a charge generating agent, an electron transfer agent and a hole transfer agent dispersed in a binder resin formed on a conductive substrate, a copolymer polycarbonate having a specified structural unit expressed by general formula (1) is used as the binder resin and at least one kind selected from a group consisting of compounds expressed by general formulae (2a) to (2u) is used as the electron transfer agent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a single-layer type organic photoconductor used in electrophotographic devices such as copying machines, facsimiles and printers.

[0002]

2. Description of the Related Art In electrophotographic devices such as copying machines, facsimiles, printers, etc., a photosensitive member is uniformly charged with a main charge,
Image exposure is performed by light irradiation based on predetermined image information to form an electrostatic latent image, the electrostatic latent image is developed, and a toner image is formed on the surface of the photoconductor. The toner image thus formed on the surface of the photoconductor is transferred to a transfer paper, and the transfer paper on which the toner image is transferred is introduced into a fixing device, and by heat and pressure,
The toner image is fixed on the transfer paper surface. On the other hand, after the transfer is completed, the toner remaining on the surface of the photoconductor is cleaned, and further, the charge is removed (irradiation of the charge removing light) if necessary.
Then, one cycle of the image forming process is completed, and the next image is formed. As a photoconductor used in such an image forming method, an organic photoconductor is widely used because it is inexpensive and easy to manufacture.

The organic photoreceptor is a single-layer type organic photoreceptor in which a photosensitive layer on a conductive substrate such as aluminum is composed of a single layer in which a charge generating agent and a charge transporting agent are dispersed in a binder resin. A multilayer organic photoreceptor comprising a laminate of a charge generating layer having a charge generating agent dispersed in a binder resin and a charge transporting layer having a charge transporting agent dispersed in the binder resin. Although known, in particular, the single-layer type organic photoreceptor can be manufactured by a simple process and is advantageous in cost.

[0004]

By the way, the organic photoconductor has a drawback that the photoconductive layer is more likely to be worn and is less durable than the inorganic photoconductors such as selenium and amorphous silicon. In particular, in the case of a single-layer type organic photoreceptor, the deterioration tendency of electrophotographic characteristics such as sensitivity due to abrasion of the photosensitive layer is more remarkable than that of the laminated type because the photosensitive layer is a single layer. , But there is a strong demand for its improvement, but no effective proposal has been made yet. For example, in order to prevent abrasion of the photosensitive layer, even if a wear-resistant binder resin is used,
Although abrasion resistance can be improved, on the other hand, there is a problem that sensitivity is significantly reduced due to abrasion (wear) of the photosensitive layer.

Therefore, the object of the present invention is to effectively suppress abrasion of the photosensitive layer, and at the same time, alleviate the tendency of deterioration of electrophotographic characteristics such as sensitivity due to abrasion of the photosensitive layer, thereby improving durability significantly. Type organic photoconductor.

[0006]

That is, according to the present invention,
In a single-layer type organic photoreceptor in which a monodisperse type photosensitive layer obtained by dispersing a charge generating agent, an electron transfer agent and a hole transfer agent in a binder resin is formed on a conductive substrate, the binder resin is , The following general formula (1):

[Chemical formula 26] In the formula, R may be the same or different, and
An alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, wherein n, m, p and q
Represents the number of substituents R that can be bonded to the ring, each of which is 0
Is a copolymerized polycarbonate having a structural unit represented by the following formula, wherein the electron transfer agent is at least selected from the group consisting of compounds represented by the following general formulas (2a) to (2u). There is provided a single-layer type organic photoconductor characterized by being one kind.

[Chemical 27] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

[Chemical 28] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl. It is a base.

[Chemical 29] In the formula, R ¹ and R ² may be the same or different,
Each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

[Chemical 30] In the formula, ^{R 1} is an alkyl group or an aryl group, having 1 to 12 carbon atoms, ^{R 2} is an alkyl group, an aryl group having 1 to 12 carbon atoms, or the formula,: -OR ³ (the carbon number of 1 ~
12 alkyl groups or aryl groups).

[Chemical 31] In the formula, R ¹ and R ² may be the same or different,
Each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, and Rs may be the same or different, and are a halogen atom and a C 1 to 12 carbon atom. An alkyl group, an alkoxy group, an aralkyl group or a phenoxy group, m represents the number of substituents R that can be bonded to the ring, and 0
Is an integer of ~ 5.

[Chemical 32] In the formula, R ¹ and R ² may be the same or different,
Each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, R ³ and R ⁴ may be the same or different, and each is a hydrogen atom, 1 to 1 carbon atoms
2 are alkyl groups, R may be the same or different, and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, or an aryl group, and m and n
Represents the number of substituents R that can be bonded to the ring, and is an integer of 0-4.

[Chemical 33] In the formula, R ^{1 to} R ⁸ may be the same or different and each represents a hydrogen atom or a nitro group, of which at least 3 are nitro groups, and R may be the same or different. Of these, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a phenoxy group, and m
Represents the number of substituents R that can be bonded to the ring, and is an integer of 0-5.

[Chemical 34] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring, R may be the same or different, and halogen An atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, m and n represent the number of substituents R that can bond to the ring, an integer of 0 to 4, and x is an integer of 1 to 4. Is.

[Chemical 35] In the formula, R ¹ and R ² may be the same or different,
R ¹ is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and R ¹
And R ² may combine with each other to form an aliphatic ring or an aromatic ring, R may be the same or different, and a halogen atom, an alkyl group having 1 to 12 carbons, and a carbon number 1 To 12 alkoxy groups, R ′, which may be the same or different, is a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. And when a group R ′ is bonded to each of the carbon atoms adjacent to each other, they may be bonded to each other to form an aliphatic ring or an aromatic ring, and m and n may be bonded to the ring. It represents the number of substituents R or R ′ and is an integer of 0 to 4.

[Chemical 36] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms,
It is an aryl group or an aralkyl group, and m and n are
The number of the substituent R which can couple | bond with a ring is shown, m is an integer of 0-4, n is an integer of 0-5, A is an oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group).

[Chemical 37] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms,
An aryl group or an aralkyl group, m, n and p
Represents the number of substituents R that can be bonded to the ring, each of 0 to
Is an integer of 4, A and B may be the same or different and are an oxygen atom, or = CR ¹ R ² (R ¹ and R
² is a cyano group or an alkoxycarbonyl group, respectively.

[Chemical 38] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms,
A cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and when the group R is bonded to each carbon atom adjacent to each other, they are bonded to each other to form an aliphatic ring or an aromatic ring. May be m, n and p
Represents the number of substituents R that can be bonded to the ring, each of 0 to
A and B, which are integers of 4, may be the same or different, and are an oxygen atom, or = CR ¹ R ² (R ¹ and R
² is a cyano group or an alkoxycarbonyl group, respectively.

[Chemical Formula 39] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms,
A cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and when the group R is bonded to each carbon atom adjacent to each other, they are bonded to each other to form an aliphatic ring or an aromatic ring. May be m, n and p
Represents the number of substituents R that can be bonded to the ring, each of 0 to
Is an integer of 4, A and B may be the same or different and are an oxygen atom, or = CR ¹ R ² (R ¹ and R
² is a cyano group or an alkoxycarbonyl group, respectively.

[Chemical 40] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring, R may be the same or different, and A lower alkyl group having a number of 4 or less, m and n represent the number of substituents R that can be bonded to the ring,
It is an integer of 0 to 8 and x is a number of 0 or 1.

[Chemical 41] In the formula, R ¹ and R ² may be the same or different,
Each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these are bonded to each other to form an aliphatic ring or aromatic group. R, which may form a ring, may be the same or different and each is a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R'is the same or different. Which may be a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and the group R ′ is bonded to each adjacent carbon atom. When these are combined, they may be bonded to each other to form an aliphatic ring or an aromatic ring, m and n are each a substituent R or R ′ which may be bonded to the ring. Are shown, m is an integer from 0 to 8, n is an integer of 0 to 4, x is the number 0 or 1.

[Chemical 42] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms,
Is an aryl group, m, n and p represent the number of substituents R that can be bonded to the ring, m is an integer of 0-4, n and p are integers of 0-5, A Is an oxygen atom, or =
CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group).

[Chemical 43] In the formula, R ¹ is a hydrogen atom, a halogen atom, or a carbon number of 1 to 8.
Is an alkyl group or an aryl group, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and m and n are rings. Shows the number of substituents R that can be bonded to, m is an integer of 0 to 4, n is 0 to
Is an integer of 5, A is an oxygen atom, or = CR ² R ³
(R ² and R ³ are each a cyano group or an alkoxycarbonyl group).

[Chemical 44] In the formula, Rs may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms,
Is an aryl group or an aralkyl group, m and n represent the number of substituents R that can be bonded to the ring, m is an integer of 0 to 4, n is an integer of 0 to 5, and A is , Oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group).

[Chemical formula 45] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an aryl group, and A and B may be the same. They may be different and are an oxygen atom or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group).

[Chemical formula 46] In the formula, each of R ¹ and R ² is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.

[Chemical 47] In the formula, each of R ¹ and R ² is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.

In the present invention, an electron transfer agent and a hole transfer agent are used together as a charge transfer agent, and a copolymerized polycarbonate having a structural unit represented by the general formula (1) is used as a binder resin. And as an electron transport agent,
It is a remarkable feature to use at least one selected from the group consisting of the compounds represented by the general formulas (2a) to (2u). That is, the copolymerized polycarbonate is a resin having excellent abrasion resistance, and the abrasion resistance of the photosensitive layer is remarkably improved by using such a resin as the binder resin. On the other hand, such a copolycarbonate is not limited to the charge generating agent and the hole transporting agent, but also the above general formula (2a) to
The affinity with the specific electron transfer agent represented by (2u) is extremely high, and as a result, the charge generation agent and the charge transfer agent (electron transfer agent, hole transfer agent) are uniformly dispersed in the binder resin. Is
It is believed that even if the thickness of the photosensitive layer is reduced by abrasion, each agent always functions stably and the deterioration of electrophotographic characteristics such as sensitivity is effectively prevented.

In the present invention, 1. The charge generating agent is mobility in the electric field strength 5 × ¹⁰ 5 V / cm is 40% or more, or the hole transport agent is mobility in the electric field strength 5 × ¹⁰ 5 V / cm, 5 × 1. ^Have a mobility of 10 ⁻⁶ cm ² / V / cm or more, The hole transport material is represented by the following general formulas (3a) to (3c).
It is preferably at least one selected from the group consisting of compounds represented by:

[0009]

[Chemical 48] In the formula, Rs may be the same or different and have 1 to 1 carbon atoms.
6 represents an alkyl group, and m, n, p, q, r and s are
Indicates the number of substituents R that can be bonded to the ring, m, n, r and s
Is an integer of 0 to 5, and p and q are integers of 0 to 4.

[Chemical 49] In the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. Is a cycloalkyl group, an aryl group, or an aralkyl group, R ³ and R ⁴ may be the same or different, and are an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R is May be the same or different, and may be an alkyl group or an alkoxy group having 1 to 6 carbon atoms,
Or when it is an aryl group and the group R is bonded to each of the carbon atoms adjacent to each other, the two R are directly linked to each other,
Alternatively, they may be bonded to each other through an oxygen atom or a sulfur atom to form a ring, m is the number of substituents R that can be bonded to the ring, is an integer of 0 to 4, and x is 0 or 0 or The number is 1.

[Chemical 50] In the formula, R ^{1 to} R ^{4, which} may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group, and R 1
Are the same or different and each is a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and m
And n represent the number of substituents R that can be bonded to the ring, and are 0 to 5
Is an integer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION [Composition of Photosensitive Layer] Binder Resin: In the present invention, as the binder resin which is a resin medium in which a charge generating agent and a charge transporting agent (electron transporting agent and hole transporting agent) are dispersed, The copolymerized polycarbonate represented by the general formula (1) is used, and the abrasion resistance of the photosensitive layer is remarkably improved by using the copolymerized polycarbonate. In the general formula (1), the substituent R capable of binding to the benzene ring is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group and an octyl group. The cycloalkyl group includes a cyclohexyl group and the like, the aryl group includes a phenyl group, a naphthyl group, a tolyl group, a xylyl group, an ethylphenyl group and the like, and the aralkyl group includes a benzyl group and phenylethyl group. Groups and the like. Further, in the above alkyl group, cycloalkyl group, aryl group and aralkyl group, a part of hydrogen atoms thereof may be substituted, and examples of such a substituent include an alkoxy group, a halogen atom and the like.

In the above copolymerized polycarbonate, the following formula (1a):

[Chemical 51] The unit A represented by the following formula (1b):

[Chemical 52] The copolymerization ratio (A / A + B) with the unit B represented by
It should be in the range of 1 to 0.4. The molecular weight is 10,000 to 20 in terms of viscosity average molecular weight (PC-A conversion).
It is preferably in the range of 10,000, particularly in the range of 18,000 to 80,000 from the viewpoint of wear resistance and the like. The proportion of the above-mentioned copolymerized polycarbonate (binder resin) in the photosensitive layer is, in particular, from the viewpoint of abrasion resistance and sensitivity characteristics described later,
A range of 50 to 70% by weight is suitable.

Charge Generating Agent: Examples of the charge generating agent dispersed in the binder resin include selenium, selenium-tellurium,
Amorphous silicon, pyrylium salt, azo pigment, disazo pigment, ansanthuron pigment, phthalocyanine pigment, indico pigment, slene pigment, toluidine pigment, pyrazoline pigment, perylene pigment, quinacridone pigment, etc. are exemplified. One kind or a mixture of two or more kinds is used so as to have an absorption wavelength region in a desired region.

In the present invention, among the charge generating agents exemplified above, those having a mobility of 40% or more at an electric field strength of 5 × 10 ⁵ V / cm are preferably used, for example, X-type metal-free. Phthalocyanine pigments such as phthalocyanine and oxotitanyl phthalocyanine, perylene pigments, and bisazo pigments are preferably used. The above-mentioned charge generating agent is 0.5 to 7% by weight based on solid content,
In particular, it is preferable that the content is 2 to 5% by weight in the photosensitive layer.

Charge Transporting Agent / Electron Transporting Agent: In the present invention, the electron transporting compounds represented by the above formulas (2a) to (2u) are selectively used as the electron transporting agent. That is,
By dispersing and blending such a specific electron-transporting agent in the binder resin of the above-mentioned polycarbonate copolymer, it is possible to effectively avoid deterioration of electrophotographic characteristics such as sensitivity due to abrasion of the photosensitive layer.

In the general formula (2a), R ^{1 to} R ⁴
May be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. As the alkyl group, a methyl group, an ethyl group,
Examples thereof include a propyl group, a butyl group, a 2-ethylhexyl group, and an octyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The cycloalkyl group includes a cyclohexyl group and the like, the aryl group includes a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an ethylphenyl group and the like, and the aralkyl group includes a benzyl group. , A phenylethyl group and the like.
Further, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, a part of hydrogen atoms thereof may be substituted, and such a substituent includes a halogen atom, a cyano group, a hydroxyl group, an amino group. , Nitro group and the like. In the compound of the general formula (2a), R ¹
To R ⁴ may all be hydrogen atoms or the same groups, but in particular, two of these groups are lower alkyl groups having 4 or less carbon atoms, and the other two are tertiary groups. A molecular chain alkyl group such as a butyl group, a cycloalkyl group, an aryl group or an aralkyl group is preferable from the viewpoint of high solubility in the organic solvent used for forming the photosensitive layer.

Suitable examples thereof include, but are not limited to, 3,5-dimethyl-3 ', 5'-di-t-butyldiphenoquinone, 3,5-dimethoxy-3', 5 '. −
Di-t-butyldiphenoquinone, 3,3'-dimethyl-
5,5'-di-t-butyldiphenoquinone, 3,5'-dimethyl-3 ', 5-di-t-butyldiphenoquinone, 3,
5,3 ', 5'-tetramethyldiphenoquinone, 2,
6,2 ', 6'-tetra-t-butyldiphenoquinone,
3,5,3 ′, 5′-tetraphenyldiphenoquinone,
3,5,3 ′, 5′-tetracyclohexyldiphenoquinone and the like can be mentioned. A typical example of the electron transfer agent represented by the general formula (2a) is a compound (ETM1) represented by the following formula.

[Chemical 53]

In the compound of the general formula (2b), R
^{1 to} R ⁴ may be the same or different, and
Hydrogen atom, C1-C12 alkyl group, C1-C1
2 is an alkoxy group, an aryl group, a cycloalkyl group, or an aralkyl group. Alkyl group, alkoxy group,
Examples of the cycloalkyl group, the aryl group, and the aralkyl group include those exemplified in the general formula (2a). Similarly, at least a part of the hydrogen atoms of these groups is a halogen atom, a cyano group, a hydroxyl group, It may be substituted with an amino group, a nitro group or the like. A typical example of the electron transfer agent represented by the general formula (2b) is a compound (ETM2) represented by the following formula.

[Chemical 54]

In the compound of the general formula (2c), R
^{1 to} R ⁴ may be the same or different, and
Hydrogen atom, C1-C12 alkyl group, C1-C1
2 is an alkoxy group, an aryl group, a cycloalkyl group, or an aralkyl group. Examples of these alkyl groups and the like include those exemplified in the general formula (2a). Similarly, at least a part of hydrogen atoms of these groups is a halogen atom, a cyano group, a hydroxyl group, an amino group, or a nitro group. It may be substituted with a group or the like. A typical example of the electron transfer agent represented by the general formula (2c) is a compound (ETM3) represented by the following formula.

[Chemical 55]

In the compound of the general formula (2d), R
¹ is an alkyl group having 1 to 12 carbon atoms or an aryl group, R ² is an alkyl group having 1 to 12 carbon atoms, an aryl group, or -OR ³ (is an alkyl group having 1 to 12 carbon atoms; A group or an aryl group). Examples of the above-mentioned alkyl group and aryl group can include those mentioned in the general formula (2a), and at least a part of hydrogen atoms of these groups is the same as a halogen atom, a cyano group, a hydroxyl group or an amino group. It may be substituted with a group, a nitro group or the like. In the compound of the general formula (2d), the group R ² is preferably —OR ³ , and particularly preferably, R ¹ is a phenyl group and R ³ is a tert-butyl group or a benzyl group. Is good. A typical example of the electron transfer agent represented by the general formula (2d) is a compound (ETM4) represented by the following formula.

[Chemical 56]

In the compound represented by the general formula (2e), R ¹ and R ² may be the same or different,
Each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, an aralkyl group or a phenoxy group, and m is the number of substituents R that can be bonded to the ring. It is shown and is an integer of 0-5. Examples of the above-mentioned alkyl group and the like can include those listed in the general formula (2a), and some hydrogen atoms of the alkyl group and the like can also be halogen atoms, cyano groups, hydroxyl groups, amino groups and nitro groups. It may be substituted with a group or the like. A typical example of the electron transfer agent represented by the general formula (2e) is a compound represented by the following formula (ET
M5).

[Chemical 57]

In the compound represented by the general formula (2f), R ¹ and R ² may be the same or different,
Each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. R ³ and R ⁴ may be the same or different and each is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, or an aryl group, and m
And n represent the number of substituents R that can be bonded to the ring, and are 0 to 4
Is an integer. Examples of the above-mentioned alkyl group and the like can include those listed in the general formula (2a), and some hydrogen atoms of the alkyl group and the like can also be halogen atoms, cyano groups, hydroxyl groups, amino groups and nitro groups. It may be substituted with a group or the like. A typical example of the electron transfer agent represented by the general formula (2f) is a compound (ETM6) represented by the following formula.

[Chemical 58]

In the compound represented by the general formula (2g), R ^{1 to} R ⁸ may be the same or different and each represents a hydrogen atom or a nitro group, of which at least 3 are nitro. It is a base. R may be the same or different and is a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a phenoxy group, and m
Represents the number of substituents R that can be bonded to the ring, and is an integer of 0-5. Examples of the above-mentioned alkyl group and the like include the general formula (2a)
Examples thereof include those mentioned above, and some hydrogen atoms such as an alkyl group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like. Typical examples of the electron transfer agent represented by the general formula (2g) are:
It is a compound (ETM7) represented by the following formula.

[Chemical 59]

In the compound of the general formula (2h), R
^{1 to} R ⁴ may be the same or different, and
Hydrogen atom, halogen atom, alkyl group or alkoxy group having 1 to 6 carbon atoms, cycloalkyl group, aryl group,
It is an aralkyl group or a heterocyclic group, and R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring. R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, m and n represent the number of substituents R that can be bonded to the ring, and Is an integer of 4,
x is an integer of 1 to 4. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, the following can be exemplified.

[Chemical 60] A part of hydrogen atoms of the alkyl group and the like and the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group and the like. General formula (2h)
A typical example of the electron transfer agent represented by is a compound (ETM8) represented by the following formula.

[Chemical 59]

In the compound of the general formula (2i), R
¹ and R ² may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. , R ¹ and R ²
May combine with each other to form an aliphatic ring or an aromatic ring. R's may be the same or different and each is a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R'may be the same or different and is a halogen atom. , A C 1-6 alkyl or alkoxy group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and when the groups R ′ are bonded to each of the carbon atoms adjacent to each other, they are mutually It may combine with each other to form an aliphatic ring or an aromatic ring. m and n represent the number of substituents R or R ′ that can be bonded to the ring, and are integers of 0 to 4. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, those exemplified in the general formula (2h) can be exemplified. And some hydrogen atoms of the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like.

A typical example of the electron transfer agent represented by the general formula (2i) is a compound represented by the following formula (ETM9).
Is.

[Chemical formula 62]

In the compound of the general formula (2j), R
Are the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group, and m and n are the number of substituents R that can be bonded to the ring. Shown, m is an integer of 0 to 4,
n is an integer of 0-5. A is an oxygen atom or a group represented by the formula: = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group). Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted. A typical example of the electron transfer agent represented by the general formula (2j) is a compound (ETM10) represented by the following formula.

[Chemical formula 63]

In the compound of the general formula (2k), R
Are the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group, and m, n and p are each a substituent R which can be bonded to a ring. The number is shown and each is an integer of 0-4. A and B may be the same or different and are an oxygen atom or a formula: = CR ¹ R ² (R ¹ and R ²
Are each a cyano group or an alkoxycarbonyl group)
Is a group represented by. Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted. A typical example of the electron transfer agent represented by the general formula (2k) is a compound represented by the following formula (ET
M11).

[Chemical 64]

In the compound of the general formula (21), R
Are the same or different, and are a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, each of which is adjacent to each other. When the groups R are bonded, they may be bonded to each other to form an aliphatic ring or an aromatic ring. m, n, and p represent the number of substituents R that can be bonded to the ring, and each is an integer of 0 to 4. A and B may be the same or different and are an oxygen atom or a formula: = CR ¹ R ² (R ¹ and R ²
Are each a cyano group or an alkoxycarbonyl group)
Is a group represented by. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, those exemplified in the general formula (2h) can be exemplified. And some hydrogen atoms of the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like.

Typical examples of the electron transfer agent represented by the general formula (21) include compounds represented by the following formula (ETM1).
2).

[Chemical 65]

In the compound of the general formula (2m), R
Are the same or different, and are a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, each of which is adjacent to each other. When the groups R are bonded, they may be bonded to each other to form an aliphatic ring or an aromatic ring. m, n, and p represent the number of substituents R that can be bonded to the ring, and each is an integer of 0 to 4. A and B may be the same or different and are an oxygen atom or a formula: = CR ¹ R ² (R ¹ and R ²
Are each a cyano group or an alkoxycarbonyl group)
Is a group represented by. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, those exemplified in the general formula (2h) can be exemplified. And some hydrogen atoms of the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like.

A typical example of the electronic transfer agent represented by the general formula (2m) is a compound represented by the following formula (ETM1).
3).

[Chemical formula 66]

In the compound of the general formula (2n), R
^{1 to} R ⁴ may be the same or different, and
Hydrogen atom, halogen atom, alkyl group or alkoxy group having 1 to 6 carbon atoms, cycloalkyl group, aryl group,
It is an aralkyl group or a heterocyclic group, and R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring. R may be the same or different and is a lower alkyl group having 4 or less carbon atoms, m and n represent the number of substituents R that can be bonded to the ring,
It is an integer of 0 to 8 and x is a number of 0 or 1. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, those exemplified in the general formula (2h) can be exemplified. And some hydrogen atoms of the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like.

A typical example of the electron transfer agent represented by the general formula (2n) is a compound represented by the following formula (ETM14
A and 14B).

[Chemical formula 67]

In the compound of the general formula (2o), R
¹ and R ² may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group. ,They are,
They may be bonded to each other to form an aliphatic ring or an aromatic ring. R may be the same or different and is a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group. R ′ may be the same or different, and are a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group,
Alternatively, when it is a heterocyclic group and the group R ′ is bonded to each of the carbon atoms adjacent to each other, these may be bonded to each other to form an aliphatic ring or an aromatic ring.
m and n represent the number of substituents R or R ′ that can be bonded to the ring, m is an integer of 0 to 8, n is an integer of 0 to 4, and x is 0 or 1. Is a number. As the above-mentioned alkyl group and the like, those exemplified in the general formula (2a) can be exemplified, and as the heterocyclic group, those exemplified in the general formula (2h) can be exemplified. And some hydrogen atoms of the heterocyclic group may be similarly substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like.

A typical example of the electron transfer agent represented by the general formula (2o) is a compound represented by the following formula (ETM1).
5).

[Chemical 68]

In the compound of the general formula (2p), R
¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. R's may be the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and m and n are substituents R capable of bonding to the ring.
, M is an integer of 0 to 4, and n is 0 to 5
Is an integer. Further, A is an oxygen atom or a formula: =
CR ² R ³ (R ² and R ³ are each a cyano group or an alkoxycarbonyl group). Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups,
It may be substituted with an amino group, a nitro group or the like.

A typical example of the electron transfer agent represented by the general formula (2p) is a compound represented by the following formula (ETM1).
6).

[Chemical 69]

In the compound of the general formula (2q), R
¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, R may be the same or different, and a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group, It is an aryl group or an aralkyl group. m and n show the number of the substituents R that can be bonded to the ring, m is an integer of 0 to 4, and n is an integer of 0 to 5. A is an oxygen atom or = CR ² R
³ (R ² and R ³ are each a cyano group or an alkoxycarbonyl group). Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted.

A typical example of the electron transfer agent represented by the general formula (2q) is a compound represented by the following formula (ETM1).
7).

[Chemical 70]

In the compound of the general formula (2r), R
Are the same or different and each is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and m and n represent the number of substituents R that can be bonded to the ring. , M is an integer of 0 to 4,
n is an integer of 0-5. A is an oxygen atom or a group represented by the formula: = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group). Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted.

A typical example of the electron transfer agent represented by the general formula (2r) is a compound represented by the following formula (ETM1).
8).

[Chemical 71]

In the compound of the general formula (2s), R
^{1 to} R ⁴ may be the same or different, and
A hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group, A and B are
They may be the same or different and may be an oxygen atom or the formula: =
CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group). Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups,
It may be substituted with an amino group, a nitro group or the like. A typical example of the electron transfer agent represented by the general formula (2s) is a compound represented by the following formula (ETM19).

[Chemical 72]

In the compound of the general formula (2t), R
Each of ¹ and R ² is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted. A typical example of the electron transfer agent represented by the general formula (2t) is a compound (ETM20) represented by the following formula.

[Chemical formula 73]

In the compound of the general formula (2u), R
Each of ¹ and R ² is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. Examples of the above-mentioned alkyl group and the like include those exemplified in the general formula (2a), and some hydrogen atoms of these alkyl groups and the like are the same as halogen atoms, cyano groups, hydroxyl groups and amino groups. , A nitro group or the like may be substituted. A typical example of the electron transfer agent represented by the general formula (2u) is a compound represented by the following formula (ETM21).

[Chemical 74]

Charge transporting agent / hole transporting agent: In the present invention, as a charge transporting agent, together with the above-mentioned specific electron transporting agent,
It is also important to use a hole transfer material, and by using such a hole transfer material together, it is possible to secure electrophotographic characteristics such as excellent sensitivity. As such a hole transporting agent, a hole transporting compound known per se can be used, but in the present invention, in particular, the above general formulas (3a) to (3) are used.
Preference is given to using the compounds represented by c). That is, the hole transporting compounds represented by these general formulas also have extremely high affinity with the binder resin of the above-mentioned polycarbonate copolymer. Therefore, when these are used in combination with the above-mentioned specific electron-transporting agent, since both the electron-transporting agent and the hole-transporting agent are uniformly dispersed in the binder resin, the thickness of the photosensitive layer may decrease due to abrasion. However, since these charge transporting properties always act at a constant rate, it is considered possible to secure constant properties such as sensitivity.

In the hole-transporting agent of the general formula (3a), R's may be the same or different and have 1 to 6 carbon atoms.
Represents an alkyl group such as methyl group, ethyl group, propyl group, primary, secondary or tertiary butyl group, heptyl group and hexyl group. In addition, these alkyl groups are
A part of the hydrogen atoms may be substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like. m,
n, p, q, r and s represent the number of substituents R that can be bonded to the ring, m, n, r and s are integers from 0 to 5, p
And q are integers of 0-4. In the present invention, a compound (HTM1) represented by the following formula can be given as a representative example of the hole transfer agent of the general formula (3a).

[Chemical 75]

In the hole-transporting agent represented by the general formula (3b), R ⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ and R ^{2, which} may be the same or different, are an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group, or an aralkyl group. R ³ and R ^{4, which} may be the same or different, are an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or an aryl group. In addition, R may be the same or different and is an alkyl group or alkoxy group having 1 to 6 carbon atoms, or an aryl group, and when the group R is bonded to each of the carbon atoms adjacent to each other, two R's are combined. May be bonded to each other directly or via an oxygen atom or a sulfur atom to form a ring, m is the number of substituents R that can be bonded to the ring, is an integer of 0 to 4, and x Is 0 or 1
Is the number of. Examples of the above-mentioned alkyl group, alkoxy group, cycloalkyl group, aryl group and aralkyl group can include those already exemplified, and also in these groups, at least a part of hydrogen atoms thereof is the same, It may be substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like. In the present invention, a compound (HTM2) represented by the following formula can be given as a representative example of the hole transfer agent of the general formula (3b).

[Chemical 76]

In the hole-transporting agent represented by the general formula (3c), R ^{1 to} R ⁴ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group.
Are the same or different and each is a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and m
And n represent the number of substituents R that can be bonded to the ring, and are 0 to 5
Is an integer. Examples of the above-mentioned alkyl group and the like include those already exemplified, and in these groups, at least a part of the hydrogen atoms thereof is substituted with a halogen atom, a cyano group, a hydroxyl group, an amino group, a nitro group or the like. It can be done. In the present invention, a compound (HTM3) represented by the following formula can be given as a representative example of the hole transfer agent of the general formula (3c).

[Chemical 77]

In the present invention, the total amount of the charge transfer material composed of the electron transfer material and the hole transfer material described above is 20 to 70% by weight, particularly 25 to 60% by weight, based on the solid content.
It is preferable that it is contained in the photosensitive layer within the range. Also, from the viewpoint of sensitivity and the wide range of applications that enable reversal development,
The weight ratio of the electron transfer material (ET) to the hole transfer material (HT) is such that the weight ratio of ET: HT is in the range of 10: 1 to 1:10, and particularly 1: 5 to 1: 1. Good.

Other compounding agents: In the present invention, various compounding agents known per se, such as biphenyl and o-, are contained in the single-layer organic photosensitive layer within a range that does not adversely affect electrophotographic characteristics. Terphenyl, m-terphenyl, p-
Biphenol derivatives such as terphenyl, p-benzylphenyl and hydrogenated terphenyl, alkyl esters such as butyl stearate, polyethylene glycol, polypropylene glycol, polyethylene glycol monoester, polyethylene glycol monoether, polyethylene glycol dialchelate, polyethylene glycol dialkyl ether Plasticizers such as polyalkyl oxides and polyphenylene oxides, lubricants, and antioxidants such as hindered amines and hindered phenols may be blended. Further, for the purpose of improving the leveling property of the formed film and imparting lubricity, a leveling agent such as silicone oil or fluorine-based oil may be contained. In particular, if the sterically hindered phenolic antioxidant is added in an amount of 0.1 to 50% by weight based on the total solid content, the durability of the photosensitive layer can be significantly improved without adversely affecting the electrophotographic characteristics. it can.

[Conductive Substrate] The photosensitive layer having the above composition is
Although formed on a conductive substrate, as the conductive substrate, various materials having conductivity can be used, for example, aluminum, copper, tin, platinum, gold, silver, vanadium, molybdenum, chromium, cadmium, Examples include simple metals such as titanium, nickel, indium, stainless steel, and brass, plastic materials in which the above metals are vapor-deposited or laminated, and glass covered with aluminum iodide, tin oxide, indium oxide, or the like. In the organic photoreceptor of the present invention, it is possible to use a normal aluminum tube or a tube that has been subjected to an alumite treatment so as to have a film thickness of 1 to 50 μm.

[Preparation of Photoreceptor] In order to form a photosensitive layer on a conductive substrate, a charge generating material, a charge transfer agent and the like and a binder resin and the like are prepared by a conventionally known method such as a roll mill, a ball mill, an attritor, or the like. It may be prepared using a paint shaker, an ultrasonic disperser, or the like, coated by a conventionally known coating means, and dried. The thickness of the photosensitive layer is not particularly limited, but it is generally preferably in the range of 10 to 50 μm, and is preferably as thick as possible within the range that does not decrease the sensitivity or increase the residual potential.

As the solvent used for forming the coating liquid, various organic solvents can be used, and alcohols such as methanol, ethanol, isopropanol and butanol,
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether, tetrahydrofuran, Ethylene glycol dimethyl ether, ethers such as diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, ketones such as cyclohexanone, ethyl acetate, esters such as methyl acetate, dimethylformamide, dimethyl sulfoxide, etc. Used as a mixture. The solid content concentration of the coating liquid is generally preferably 5 to 50%.

The photosensitive layer may be formed directly on the conductive substrate, but may be formed via an undercoat layer. Examples of such an undercoat layer include polymer films of casein, polyvinyl alcohol, polyvinyl acetal, polyamide, melamine, cellulose, polythiophene, polypyrrole, polyaniline, polyester, polyacrylate, polystyrene and the like. The thickness of the undercoat layer is preferably in the range of 0.01 μm to 20 μm. Further, in order to impart conductivity to the undercoat layer, metal powder such as gold, silver and aluminum, metal oxide powder such as titanium oxide and tin oxide, and conductive fine powder such as carbon black can be dispersed.

The single-layer type organic photoconductor of the present invention thus obtained has not only excellent abrasion resistance, but also when the thickness of the photosensitive layer is reduced due to abrasion, electrophotographic characteristics such as sensitivity tend to deteriorate. Is extremely small and exhibits excellent durability. Therefore, such a photoreceptor can be effectively applied to image formation in an electrophotographic apparatus such as a copying machine, a facsimile, a printer, and the like.

[0056]

The present invention will be described in the following experimental examples.

Preparation of Photoreceptor: Charge Generating Agent, Electron Transfer Agent,
The following were used as the hole transport material and the binder. Charge generator: X-type metal-free phthalocyanine Electron transfer agent: Compounds of the following formulas as comparative examples of the compounds of ETM1 to 21 described above

[Chemical 78] Hole transport agent: Compound of HTM1 to 3 described above Binder resin: Represented by the following formula and having a viscosity average molecular weight of 50,0
00 polycarbonate copolymer (resin 1).

[Chemical 79] As a comparative example, a polycarbonate copolymer (resin 2) represented by the following formula.

[Chemical 80]

The above charge generating agent, electron transporting agent, hole transporting agent and binder resin are blended in the combinations shown in Table 1 in the following weight ratios and dissolved in an organic solvent to prepare a photosensitive layer forming coating solution. Was prepared. Charge generating agent 2.5 parts by weight Electron transporting agent 33 parts by weight Hole transporting agent 62 parts by weight Binder resin 100 parts by weight By applying the coating solution prepared above to an aluminum tube having a diameter of 30 mm and drying. A photosensitive layer having a thickness of about 24 μm was formed. The obtained single-layer type organic photoreceptor was evaluated as follows, and the results are shown in Tables 1 to 4.

Evaluation method [Abrasion resistance evaluation test] The single-layer type photoconductors of the above Examples and Comparative Examples were mounted on a copying machine having a blade cleaning means ("Creage 7340" manufactured by Kyocera Mita Co., Ltd.) to form an image. (No toner development, no paper passing),
While the cleaning blade was pressed against the photosensitive drum, the photosensitive drum was continuously rotated for 72 hours. Then, the film thickness of the photosensitive layer before and after the test was measured, and the film thickness change amount was calculated. The smaller the change in film thickness, the better the wear resistance. The amount of change in film thickness was allowed to be 3.0 μm or less, and not allowed to be greater than 3.0 μm. [Initial Sensitivity Evaluation Test] Using a drum sensitivity tester manufactured by GENTEC, each example before the above abrasion resistance test evaluation,
An applied voltage was applied to the surface of the single-layer type photoreceptor of the comparative example to charge the surface to + 700V. Then, monochromatic light with a wavelength of 780 nm (half-value width of 20 n is extracted from white light of a halogen lamp which is an exposure light source using a bandpass filter.
m, 1.0 μJ / cm ² ) and exposed to 0.
The surface potential after 5 seconds was measured as an initial residual potential (V _0L ). The lower the residual potential, the higher the sensitivity of the photoreceptor. 150V for initial residual potential
The case where it is smaller than that is acceptable, and the case where 150 V or more is not acceptable. [Sensitivity change rate] Residual potential (V _1L ) of each single-layer type photoreceptor of each Example and Comparative Example after abrasion resistance test evaluation (after 72 hours)
Was measured in the same manner as in the initial sensitivity evaluation test, and the rate of change in sensitivity (ΔV _L ) was calculated by the following formula. The smaller the rate of change in sensitivity, the smaller the change in sensitivity of the photoreceptor and the excellent durability. Sensitivity change rate ΔV _L (%) = (V _1L −V _0L ) / V _0L
× 100

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

INDUSTRIAL APPLICABILITY According to the present invention, abrasion resistance is improved by using a specific polycarbonate copolymer as a binder resin, and by using a specific electron transfer agent in combination with a hole transfer agent as a charge transfer agent. In addition, a single-layer type organic photoconductor was obtained which was excellent in durability and in which the deterioration of electrophotographic characteristics such as sensitivity due to the reduction of the thickness of the photosensitive layer due to abrasion was remarkably suppressed, and the durability was remarkably improved.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ayako Yajima             Kyocera 1-22-28 Tamatsukuri, Chuo-ku, Osaka-shi             Within Mita Co., Ltd. F term (reference) 2H068 AA13 AA18 AA20 AA31 BA12                       BA13 BA16 BB26

Claims (4)

[Claims] 1. A single-layer type organic photoreceptor in which a monodisperse type photosensitive layer formed by dispersing a charge generating agent, an electron transferring agent and a hole transferring agent in a binder resin is formed on a conductive substrate. The binder resin has the following general formula (1): In the formula, R may be the same or different and each is an alkyl group having 18 or less carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and n, m, p and q can be bonded to a ring. A copolymeric polycarbonate having a structural unit represented by the number of substituents R, each of which is an integer of 0 to 4, wherein the electron transfer agent is represented by the following general formulas (2a) to (2u). A single-layer type organic photoconductor, which is at least one selected from the group consisting of the following compounds: In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. 3] In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 12 carbons, or a carbon number 1
Is an alkoxy group, a cycloalkyl group, an aryl group, or an aralkyl group represented by: In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. 5] In the formula, ^{R 1} is an alkyl group or an aryl group, having 1 to 12 carbon atoms, ^{R 2} is an alkyl group, an aryl group having 1 to 12 carbon atoms, or the formula,: -OR ³ (the carbon number of 1 ~ 12 alkyl groups,
Or an aryl group) is a group represented by: In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R is , Which may be the same or different, are a halogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, an aralkyl group or a phenoxy group, and m represents the number of the substituents R which can be bonded to the ring, and 0 to Is an integer of 5, In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ³ And R ⁴ may be the same or different and each is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R may be the same or different, a halogen atom or an alkyl group having 1 to 12 carbon atoms. A group or an alkoxy group, or an aryl group, m and n represent the number of substituents R that can be bonded to the ring, and 0 to
Is an integer of 4, In the formula, R ^{1 to} R ⁸ may be the same or different and each represents a hydrogen atom or a nitro group, of which at least 3 are nitro groups, and R may be the same or different. Well, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, an aryl group, an aralkyl group or a phenoxy group, m represents the number of substituents R that can be bonded to the ring, Is an integer of 0 to 5, In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. A cyclic group, R ¹ and R ²
Alternatively, R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring. Rs may be the same or different, and are a halogen atom or an alkyl group having 1 to 12 carbon atoms. Or an alkoxy group, m and n represent the number of substituents R that can be bonded to the ring, and
Is an integer of 4, x is an integer of 1 to 4, embedded image In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. A cyclic group, R ¹ and R ²
May be bonded to each other to form an aliphatic ring or an aromatic ring. Rs may be the same or different and each is a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It is an alkoxy group, R ′ may be the same or different, and a halogen atom,
An alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and when a group R ′ is bonded to each adjacent carbon atom, these are bonded to each other. May form an aliphatic ring or an aromatic ring, and m and n represent the number of the substituents R or R ′ that can be bonded to the ring, and are an integer of 0 to 4, In the formula, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group, and m and n are substituents that can bond to the ring. The number of R is shown, m is an integer of 0-4, n is an integer of 0-5, A is an oxygen atom, or = CR ¹ R ² (R ¹ and R
^{And 2} is a cyano group or an alkoxycarbonyl group, respectively. In the formula, R, which may be the same or different, is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group, or an aralkyl group, and m, n, and p can be bonded to a ring. Shows the number of substituents R,
Each is an integer of 0 to 4, A and B may be the same or different, and an oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group); In the formula, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and carbons adjacent to each other. When the group R is bonded to each atom, they may be bonded to each other to form an aliphatic ring or an aromatic ring, and m, n and p are the number of substituents R that can be bonded to the ring. Indicates
Each is an integer of 0 to 4, A and B may be the same or different, and an oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group); In the formula, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and carbons adjacent to each other. When the group R is bonded to each atom, they may be bonded to each other to form an aliphatic ring or an aromatic ring, and m, n and p are the number of substituents R that can be bonded to the ring. Indicates
Each is an integer of 0 to 4, A and B may be the same or different, and an oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group); In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. A cyclic group, R ¹ and R ²
Alternatively, R ³ and R ⁴ may be bonded to each other to form an aliphatic ring or an aromatic ring. Rs may be the same or different and each is a lower alkyl group having 4 or less carbon atoms, m and n represent the number of substituents R that can be bonded to the ring, and
Is an integer of 8, x is a number of 0 or 1, embedded image In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a hetero group. A cyclic group, which may be bonded to each other to form an aliphatic ring or an aromatic ring. R's may be the same or different and each is a halogen atom, an alkyl group having 1 to 12 carbon atoms, or It is an alkoxy group, R ′ may be the same or different, and a halogen atom,
An alkyl group or an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and when a group R ′ is bonded to each of the carbon atoms adjacent to each other, these are: They may be bonded to each other to form an aliphatic ring or an aromatic ring. M and n represent the number of substituents R or R ′ that can be bonded to the ring, and m is an integer of 0 to 8. , N is an integer of 0 to 4, x is a number of 0 or 1, embedded image In the formula, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an aryl group, and m, n and p are the substituents R that can bond to the ring. Shows the number,
m is an integer of 0 to 4, n and p are integers of 0 to 5, A is an oxygen atom, or = CR ¹ R ² (R ¹ and R
² are each a cyano group or an alkoxycarbonyl group), In the formula, R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, R may be the same or different, and a halogen atom, an alkyl group having 1 to 8 carbon atoms Or an alkoxy group, an aryl group or an aralkyl group, m and n represent the number of substituents R that can be bonded to the ring, and m
Is an integer of 0 to 4, n is an integer of 0 to 5, A is an oxygen atom, or = CR ² R ³ (R ² and R
^{And 3} is a cyano group or an alkoxycarbonyl group, respectively. In the formula, R may be the same or different and is a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, an aryl group or an aralkyl group, and m and n are substituents R that can bond to the ring. The number of m
Is an integer of 0 to 4, n is an integer of 0 to 5, A is an oxygen atom, or = CR ¹ R ² (R ¹ and R
^{And 2} is a cyano group or an alkoxycarbonyl group, respectively. In the formula, R ^{1 to} R ⁴ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an aryl group, and A and B may be the same. May be different, oxygen atom,
Or = CR ¹ R ² (R ¹ and R ² are each a cyano group or an alkoxycarbonyl group); In the formula, each of R ¹ and R ² is an alkyl group having 18 or less carbon atoms,
A cycloalkyl group, an aryl group, or an aralkyl group, In the formula, each of R ¹ and R ² is an alkyl group having 18 or less carbon atoms,
It is a cycloalkyl group, an aryl group or an aralkyl group. 2. The electric charge generating agent has an electric field intensity of 5 × 10 ^5.
The single-layer organic photoreceptor according to claim 1, which has a mobility of 40% or more at V / cm. 3. The hole transport material has an electric field strength of 5 × 10 ^5.
The mobility at V / cm is 5 × 10 ⁻⁶ cm ² / V /
The single-layer type organic photoconductor according to claim 1, which has a mobility of cm or more. 4. The hole transport material is represented by the following general formula (3a):
A single-layer type organic photoconductor according to claim 3, which is at least one selected from the group consisting of compounds represented by (3c) to (3c); In the formula, R may be the same or different and represents an alkyl group having 1 to 6 carbon atoms, and m, n, p, q, r and s are substituents R that can bond to the ring.
, M, n, r and s are integers of 0 to 5, p and q
Is an integer from 0 to 4, In the formula, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹ and R ² may be the same or different, and are an alkyl group having 1 to 12 carbon atoms and 3 to 12 carbon atoms. Is a cycloalkyl group, an aryl group, or an aralkyl group, R ³ and R ^{4, which} may be the same or different, are an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and R is They may be the same or different and are an alkyl group or an alkoxy group having 1 to 6 carbon atoms, or an aryl group, and when a group R is bonded to each of the carbon atoms adjacent to each other, two Rs are directly bonded to each other, or They may be bonded to each other via an oxygen atom or a sulfur atom to form a ring, m is the number of substituents R that can be bonded to the ring, is an integer of 0 to 4, and x is 0 or 1 Is the number of, 25] In the formula, R ^{1 to} R ⁴ may be the same or different and have 1 carbon atom.
To R 6 are alkyl groups or aralkyl groups, R may be the same or different, and are a halogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and m and n are substituents capable of bonding to the ring. Indicates the number of groups R, 0 to
It is an integer of 5.