JPH06332220A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body to be positively charged excellent in sensitivity and residual potential characteristic and capable of forming a distinct and residual potential fog even after the repeated formation of images over a long period by incorporating a specified electron acceptive substance into the protective layer on the surface of a photosensitive layer. CONSTITUTION:A protective layer contg. an electron acceptive substance shown by the formula is provided on the surface of a photosensitive layer. In the formula, RA is hydrogen atom, hydroxyl, nitrogroup, CF3 group, alkyls, alkoxyls, aryls, etc., and (l), (m) and (n) are 0 or a positive integer respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor,
In particular, the present invention relates to a positive charging photoreceptor having an improved protective layer.

[0002]

2. Description of the Related Art Conventionally, an electrophotographic photosensitive member using an organic photoconductive material has advantages such as no pollution, low cost and high productivity. It is used as a photoconductor and is being put into practical use as a photoconductor for high-speed copying machines.

In order to ensure high-performance electrophotographic performance, the photoreceptor contains a charge generating material (CGM) having a function of generating electric charges and a charge transporting material (CTM) having a function of transferring electric charges. It is preferable to use a photoconductor.
The photoconductor has a single layer constitution type in which CGM and CTM coexist in the photosensitive layer or a charge transport layer (CTL) containing CTM as a main component and a charge generation layer (CGL) containing CGM. There is a function-separated type photoreceptor having a layer structure.

CTM contained in the function-separated type photoreceptor
As a conventional method, many P-type CTMs having excellent hole transporting functions have been developed.

Therefore, a negatively-charged photoreceptor having a CGL containing CGM having an excellent charge generating function as a lower layer and a CTL containing P-type CTM having an excellent hole transporting function as an upper layer has been mainly used.

However, the above-mentioned photoconductor has a problem that a large amount of ozone is generated at the time of negative electrification, which not only harms the environment, but also deteriorates the photoconductor surface to cause fatigue deterioration.

Therefore, by reversing the layer structure of the photoreceptor, C
Research and development of a photoconductor having a two-layer structure for positive charging, in which TL is the lower layer and CGL is the upper layer, is underway. Further, since the photoreceptor having the single-layer structure uses the P-type CTM as the CTM, the electrophotographic performance is better when used for positive charging than when used for negative charging.

However, all of these photoreceptors are CG
Since M is present in the surface layer of the photoconductor, there is a problem that the photoconductor is easily fatigue-degraded due to deterioration or abrasion due to light, corona discharge, humidity, mechanical rubbing, or the like.

Therefore, for example, it is proposed to provide a protective layer of an insulating and transparent resin, and at the time of light irradiation, the protective layer contains an electron-accepting substance so as to prevent the blocking of charges by the protective layer. The technology which was done is proposed.

For example, JP-A-62-157047 discloses a technique of providing a protective layer containing an electron-accepting substance on a positive charging photoreceptor having a conductive support and CTL and CGL provided in this order. Proposed. Further, in the above-mentioned publication, since the electron-accepting substance has an electron-transporting function, photoelectrons generated at the time of light irradiation can move quickly in the protective layer, and the surface positive charges of the photoconductor can be effectively canceled, resulting in a high-quality image. Is obtained.

[0011]

However, the conventionally known electron-accepting substance does not always have a sufficient electron-transporting function, so that the protective layer must be thinned.
Mechanical wear resistance becomes insufficient. Even if it has a relatively excellent electron-transporting function, it has poor solubility in a binder resin or a solvent, the original electron-transporting function is not exhibited, and the distribution of the electron-accepting substance in the protective layer is poor. Be uniform. Therefore, the charge generated during light irradiation is blocked in the protective layer and the surface charge of the photoconductor is not dissipated, resulting in an image with a lot of fog. Was causing problems such as bad.

[0012] Therefore, recently known as an electron-accepting substance,
Improvement studies on 4,7-trinitro-9-fluorenone have been carried out, and a technique of introducing a solubilizing group into the structure of the compound to increase the compatibility with the binder resin and the solvent to improve the properties has been described in, for example, Kaihei 1-206349, 2-135362, 2-2148
Nos. 66 and 3-290666, and "Japam Hardcopy,"
92 papers, 173, (1922) ”, etc.

However, when any of the compounds described in the above publications and documents is used for the protective layer of the positive charging photoreceptor, the photoreceptor fatigue deteriorates in the course of repeated image formation,
I was not satisfied.

The present invention has been proposed in view of the above circumstances, and an object of the present invention is that it is excellent in charging characteristics, light attenuation characteristics, residual potential characteristics, and the like, and does not generate ozone during image formation. Another object of the present invention is to provide a photoconductor for positive charging, which has excellent printing durability and is free from fatigue deterioration during repeated image formation.

[0015]

The above object is to provide an electrophotographic photoreceptor having a photosensitive layer provided on a conductive support and a protective layer provided on the photosensitive layer. , "Chemical 23,""Chemical24,""Chemical2"
5 ”,“ 26 ”,“ 27 ”,“ 28 ”,“ 29 ”,“ 3 ”
0 ”,“ Chemical formula 31 ”,“ Chemical formula 32 ”,“ Chemical formula 33 ”, the general formulas [A], [B], [C], [D], [E], [F],
This is achieved by each electrophotographic photosensitive member containing any of the compounds represented by [G], [H], [J], [K] and [L].

[0016]

[Chemical formula 23]

In the formula, R _A is a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, a COOR _A ′ group, an OCOR _A ′.
Group, CONH ₂ group, CONHR _A ′ group, CON (R _A ′) ₂
Group, COR _A 'group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R _A' represents an alkyl group which may have a substituent, an aryl group Alternatively, it represents an aralkyl group.
l, m and n each represent 0 or a positive integer, and l is 0
In the case of, m represents an integer of 2 or more, and when 1 is an integer of 1 or more, m represents 0 or a positive integer. The plural groups represented by R _A may be the same or different.

[0018]

[Chemical formula 24]

In the formula, Y _B represents a cyano group or a CF ₃ group,
R _B is a halogen atom, hydroxy group, nitro group, CF
₃ group, COOR _B 'group, OCOR _B' group, CONH ₂ group, C
ONHR _B ′ group, CON (R _B ′) ₂ group, COR _B ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R _B ′ is substituted Represents an alkyl group, an aryl group or an aralkyl group which may have a group. l, m and n each represent an integer of 1 or more. The plural groups of Y _B and R _B may be the same or different.

[0020]

[Chemical 25]

[0021] In the formula, X _C is COOR _C 'group, OCOR _C'
Group, CONH ₂ group, CONHR _C ′ group, CON (R _C ′) ₂
Group, a COR _C ′ group or a CHO group, and Y _C is a halogen atom, a cyano group, a nitro group, a CF ₃ group, a COOH group, SO ₂
NH ₂ group, SO ₂ R _C ′ group or SOR _C ′ group, wherein R _C is a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, C
OOR _C ′ group, OCOR _C ′ group, CONH ₂ group, CONH
R _C ′ group, CON (R _C ′) ₂ group, COR _C ′ group or alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group which may have a substituent,
_C 'represents an optionally substituted alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X _C , Y _C and R _C may be the same or different.

[0022]

[Chemical formula 26]

In the formula, X _D is a COOH group, SO ₂ NH ₂ group,
Represents a SOR _D ′ group or a SO ₂ R _D ′ group, Y _D represents a halogen atom, a cyano group, a nitro group or a CF ₃ group, and R _D represents a halogen atom, a hydroxy group, a nitro group, a CF ₃ group or COO
R _D ′ group, OCOR _D ′ group, CONH ₂ group, CONHR _D ′
Group, CON (R _D ′) ₂ group, COR _D ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, and R _D ′ has a substituent group. Represents an alkyl group, an aryl group or an aralkyl group which may be present. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more.
The plural groups of X _D , Y _D and R _D may be the same or different.

[0024]

[Chemical 27]

In the formula, X _E represents a halogen atom, Y _E represents a cyano group, a nitro group or a CF ₃ group, and R _E represents a halogen atom, a hydroxy group, a nitro group, a CF ₃ group or COOR _E ′.
Group, OCOR _E ′ group, CONH ₂ group, CONHR _E ′ group,
A CON (R _E ′) ₂ group, a COR _E ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, R _E ′ having a substituent group Represents an alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X _E , Y _E and R _E may be the same or different.

[0026]

[Chemical 28]

In the formula, X _F is a halogen atom, a cyano group, a nitro group, a CF ₃ group, a COOH group, a COOR _F ′ group, or an OCO.
R _F ′ group, CONH ₂ group, CONHR _F ′ group, CON
(R _F ′) ₂ group, COR _F ′ group, SO ₂ NH ₂ group, SOR _F ′
Group, SO ₂ R _F ′ group or CHO group, Y _F represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R _F represents a halogen atom, a hydroxy group, a nitro group or CF ₃ group, COOR _F 'group, OCOR _F' group, CON
H ₂ group, CONHR _F ′ group, CON (R _F ′) ₂ group, COR
_F 'group or an alkyl group which may have a substituent, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R _F' is an optionally substituted alkyl group, an aryl group or an aralkyl group Represents The plural groups of X _F , Y _F and R _F may be the same or different.

[0028]

[Chemical 29]

In the formula, Y _1G represents an alkyl group which may have a substituent, R _2G represents a halogen atom, a hydroxy group, a cyano group, a nitro group, an N (R _G ′) ₂ group, an OR _G ′ group. , COO
R _G ′ group, OCOR _G ′ group, COR _G ′ group, CONHR _G ′
Group, CON (R _G ′) ₂ group, SOR _G ′ group, SO ₂ R _G ′ group, or an aryl group or aralkyl group which may have a substituent, and R _G ′ may have a substituent. Represents a good alkyl group, aryl group or aralkyl group. l represents 0 or a positive integer, m represents an integer of 2 or more, and n represents an integer of 1 or more. The plurality of Y _1G and R _2G groups may be the same or different.

[0030]

[Chemical 30]

In the formula, X _H is a hydroxy group, an OR _H ′ group, N
(R _H ′) ₂ group or an optionally substituted alkyl group, aryl group or aralkyl group, Y _H is a halogen atom, a cyano group, a nitro group, a CF ₃ group, a COR _H ′ group, C
OOR _H ′ group, OCOR _H ′ group, CONHR _H ′ group, CO
Represents an N (R _H ′) ₂ group, a SOR _H ′ group or a SO ₂ R _H ′ group, R _H represents an _optionally substituted alkyl group or an aralkyl group, and R _H ′ has a substituent. Represents an alkyl group or an aryl group which may be present. l represents 0 or a positive integer,
m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plural groups of X _H , Y _H and R _H ′ may be the same or different.

When the substituent in the above formula [H] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cyclic unless otherwise specified. Or an alkyl group which may contain an unsaturated bond (eg, methylethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group,
Hydroxyethyl group, methoxyethyl group, phenoxyethyl group).

When the substituent in the above formula [H] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).

[0034]

[Chemical 31]

In the formula, X _J is a hydroxy group, OR _J ′ group, N
(R _J ′) ₂ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent, and Y _J and R _F are a halogen atom, a cyano group, a nitro group, a CF ₃ group and COOR _J ′.
Group, OCOR _J ′ group, CONHR _J ′ group, SOR _J ′ group or SO ₂ R _J ′ group, R _J ′ represents an optionally substituted alkyl group, aryl group or aralkyl group, and A Represents an atomic group necessary for forming a condensed polycyclic aromatic carbocycle. l, m and n represent 0 or a positive integer, and n + m is 2
The above integers are represented, and l + m represents an integer of 2 to 8. The plural groups of X _J , Y _J and R _F may be the same or different.

When the substituent in the above general formula [J] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked, unless otherwise specified. An alicyclic ring, which may be substituted or may contain an unsaturated bond (for example, a methyl group, an ethyl group, an iso-propyl group, a t-butyl group, a pentyl group, a 2-ethylhexyl group, Dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).

When the substituent in the above formula [J] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).

[0038]

[Chemical 32]

In the formula, X _K is a hydroxy group, an OR _K ′ group, N
(R _K ′) ₂ represents an alkyl group, an aryl group or an aralkyl group which may have a substituent, and Y _K and R _K are a halogen atom, a cyano group, a nitro group, a CF ₃ group and a COR _K ′.
Group, COOR _K ′ group, OCOR _K ′ group, CONHR _K ′
Group, SOR _K ′ group or SO ₂ R _K ′ group, R _K ′ represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and B represents an aliphatic ring together with the carbon atom of the benzene ring. Represents a hydrocarbon atom group necessary for forming. l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. There are multiple R
_The groups _{K 1} , Y _K and R _K may be the same or different.

When the substituent in the general formula [K] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked unless otherwise specified. An alicyclic ring, which may be substituted or may contain an unsaturated bond (for example, a methyl group, an ethyl group, an iso-propyl group, a t-butyl group, a pentyl group, a 2-ethylhexyl group, Dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).

When the substituent in the above general formula [K] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).

[0042]

[Chemical 33]

In the formula, X _L is a hydroxy group, OR _L' group, N
( _RL ') ₂ group or an optionally substituted alkyl group, aryl group or aralkyl group, wherein Y _L and R _L are a halogen atom, a cyano group, a nitro group, a CF ₃ group and COR _L '
Group, COOR _L ′ group, OCOR _L ′ group, CONHR _L ′
Group, a SOR _L 'groups or SO ₂ R _L' group, R _L 'is an optionally substituted alkyl group, an aryl group or an aralkyl group, D a is necessary to form a heterocyclic non Represents a group of metal atoms. l, m and n represent 0 or a positive integer, m +
n represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The groups X _L , Y _L , and R _L may be the same or different.

When the substituent in the above formula [L] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or crosslinked unless otherwise specified. An alkyl group which is an alicyclic ring and may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group,
Pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group,
Methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group).

When the substituent in the above formula [L] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and is a monocyclic or condensed ring aryl group. (For example, phenyl group, 1-
Naphthyl group, p-tolyl group, p-chlorophenyl group, 4
-Methoxyphenyl group, pentafluorophenyl group, p
-Hydroxyphenyl group, p-cyanophenyl group, p-
Methanesulfonamide phenyl group, 3,4-dichlorophenyl group).

In a preferred embodiment of the present invention, there are provided general formulas [a] to [l] corresponding to the general formulas [A] to [L], respectively, which are structurally restricted. Included are the compounds shown.

In the photoconductor of the present invention, a two-layer photoconductor having P-type CTM and CTL optionally containing a binder resin as a lower layer, and CGM and optionally CGL containing P-type CTM and a binder resin as an upper layer. On a layer,
A protective layer is provided which uniformly contains an electron-accepting substance peculiar to the present invention having an excellent electron-transporting function.

Further, in the photoreceptor of the present invention, CGM and P-type CT
A protective layer containing the electron-accepting substance may be provided on the photosensitive layer having a single-layer structure containing M and, if necessary, a binder resin.

The photoconductor thus constructed is for positive charging, and when holes and electrons are generated on the photosensitive layer during light irradiation, the holes are promptly transferred to the substrate side through the P-type CTM in the photosensitive layer. As the electrons move, the electrons rapidly move to the surface layer by the action of the electron-accepting substance in the protective layer, and the positive charge of the surface layer is canceled. Thus, even if the protective layer is provided, high sensitivity, electrophotographic characteristics excellent in residual potential characteristics are obtained, and high durability is exhibited.

Specific examples and synthetic examples of the electron-accepting substance contained in the protective layer of the positive charging photoreceptor of the present invention are as follows.

[0051]

Next, specific examples of the compounds represented by the above general formulas [A] to [L] and synthetic examples thereof will be shown.

Exemplary compounds represented by the general formula [A]:

[0053]

[Chemical 34]

(Numbers 1 to 13 in the above general formula indicate the positions of the substituents.)

[0055]

[Chemical 35]

[0056]

[Chemical 36]

Synthesis example

[0058]

[Chemical 37]

Exemplified Compound A-16 was synthesized according to the above synthetic route. Using 2,5-bis (trifluoromethyl) aniline (manufactured by Aldrich) as a starting material, a known method (J.Ch
Compound 4 was synthesized according to em, Soc, 1071-6 (1954)).

10 g of compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, an ester tube and a thermometer were attached, and 50 Heated to reflux for hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 9.5 g of red powder of Exemplified Compound A-16 (yield 75
%) Was obtained. The melting point was measured by the Japanese Pharmacopoeia melting point measurement method and was found to be 153-155 ° C. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound A-16 was confirmed.

C H N calculated value 59.15% 2.90% 2.87% Measured value 58.51% 3.01% 2.73% Exemplified compound represented by the general formula [B]: The method for indicating the position of the substituent is the same as the general formula [A].

[0062]

[Chemical 38]

[0063]

[Chemical Formula 39]

Synthesis example

[0065]

[Chemical 40]

Exemplified Compound B-2 was synthesized according to the above synthetic route. Using 2-iodobenzotrifluoride (manufactured by Aldrich) as a starting material, a known method (J. Chem, So
c, 1071-6 (1954)), compound 4 was synthesized.

10 g of compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 50 hours. After cooling, the solid is removed by suction filtration and washed well with ethyl acetate and chloroform. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The eluate of toluene: n-hexane = 1: 1 was crystallized with n-hexane to obtain 8.5 g (yield 64%) of a red powder of Exemplified Compound B-2. The melting point was 189 to 190 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, Exemplified Compound B
-2 structure was confirmed.

C H N calculated value 59.87% 3.20% 9.52% measured value 59.71% 3.31% 9.40% Exemplified compound represented by the general formula [C]: The method for indicating the position of the substituent is the same as the general formula [A].

[0069]

[Chemical 41]

[0070]

[Chemical 42]

[0071]

[Chemical 43]

Synthesis example

[0073]

[Chemical 44]

Exemplified Compound C-1 was synthesized according to the above synthetic route. Using 9-fluorenone-4-carboxylic amide (manufactured by Aldrich) as a starting material, according to a conventional method,
Compound 3 was synthesized.

10 g of compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 50 hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 6.8 g of Exemplified Compound C-1 red powder (yield 56
%) Was obtained. The melting point was 193-196 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound C-1 was confirmed.

C H N calculated value 68.04% 5.90% 7.93% Actual value 67.59% 6.05% 7.72% Exemplified compound represented by the general formula [D]: The method for indicating the position of the substituent is the same as that of the general formula [A].

[0077]

[Chemical formula 45]

[0078]

[Chemical formula 46]

Synthesis example

[0080]

[Chemical 47]

Exemplified Compound D-2 was synthesized according to the above synthetic route. Compound 1 as a starting material, the known methods (J.
Compound 4 was synthesized according to Chem, Soc, 1071-6 (1954)).

10 g of Compound 4 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2-ethylaniline 5 (manufactured by Aldrich) and 100 ml of ODB were added, and the mixture was heated under reflux for 120 hours with an ester tube and a thermometer attached. . After allowing to cool, the solid is removed by suction filtration and washed well with DMSO. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 9: 1 eluate was crystallized from toluene to give 9.9 g of a dark red powder of Exemplified Compound D-2 (yield 78
%) Was obtained. The melting point was 193-194 ° C. as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound D-2 was confirmed.

C H N calculated value 56.80% 3.97% 2.76% Actual value 56.62% 4.01% 2.51% Exemplified compound represented by the general formula [E]: The method of displaying substituents is the same as that of the general formula [A].

[0084]

[Chemical 48]

[0085]

[Chemical 49]

Synthesis example

[0087]

[Chemical 50]

Exemplified compound E-1 was synthesized according to the above synthetic route. A known method using 2,4,7-trinitrofluorenone (manufactured by Aldrich) as a starting material is disclosed in JP-A 1-2906.
No. 54), compound 2 was synthesized.

10 g of compound 2 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2-ethylaniline 3 (manufactured by Aldrich) and 100 ml of ODB were added, and the mixture was heated under reflux for 60 hours with an ester tube and a thermometer attached. did. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 6.8 g of red powder of Exemplified Compound E-1 (yield 52
%) Was obtained. The melting point was 176 to 178 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound E-1 was confirmed.

C H N calculated value 55.77% 3.12% 9.29% measured value 55.72% 3.14% 9.10% Exemplary compound represented by general formula [F]:

[0091]

[Chemical 51]

[0092]

[Chemical 52]

[0093]

[Chemical 53]

Synthesis example

[0095]

[Chemical 54]

Exemplified compound F-1 was synthesized according to the above synthetic route. Known method using 3-methyl-4-aminobenzonitrile as a starting material (J. Chem, Soc, 1071-6 (1954))
According to the above, compound 4 was synthesized.

Compound 4 ; 10 g was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 2,6-xylidine 5 (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached. The mixture was heated under reflux for 75 hours. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 11.9 g of brown crystals of the exemplified compound F-1 (yield
84%). The melting point was measured in accordance with the Japanese Pharmacopoeia melting point measurement method and was found to be 159 to 160 ° C. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound F-1 was confirmed.

C H N calculated value 82.97% 4.93% 12.09% Measured value 82.93% 4.95% 12.03% Exemplified compound represented by general formula [G]: The method of displaying substituents is the same as in general formula [A].

[0099]

[Chemical 55]

[0100]

[Chemical 56]

Synthesis example

[0102]

[Chemical 57]

Exemplified Compound G-1 was synthesized by the above reaction.

That is, 10 g of 2,4,7-trifluorenone 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 100 ml four-headed flask, and zinc chloride 20
g and 2-aminobiphenyl 2 (made by Aldrich) 10 g and O
DB100 ml was added, and the mixture was heated under reflux for 80 hours with an ester tube and a thermometer attached. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from toluene to obtain 12.1 g (yield 81%) of red crystals of Exemplified Compound G-1. The melting point was 181 to 183 ° C as measured by the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of Exemplified Compound G-1 was confirmed.

C H N calculated value 64.38% 3.03% 12.01% measured value 64.21% 3.07% 11.92% exemplary compound represented by general formula [H]:

[0106]

[Chemical 58]

[0107]

[Chemical 59]

[0108]

[Chemical 60]

[0109]

[Chemical formula 61]

Synthesis example

[0111]

[Chemical formula 62]

Exemplified Compound H-1 was synthesized according to the above synthetic route. Compound 3 was synthesized according to a known method (J. Chem, Soc, 1071 to 6 (1954)) using 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) as a starting material.

10 g of Compound 3 was placed in a 100 ml four-headed flask, and 20 g of zinc chloride, 5 g of t-octylamine 4 (manufactured by Aldrich) and o-dichlorobenzene (hereinafter abbreviated as ODB).
100 ml was added, and the mixture was heated under reflux for 55 hours with an ester tube and a thermometer attached. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. Toluene: n-hexane =
The 1: 1 eluate was crystallized with n-hexane to obtain 7.9 g (yield 61%) of a red powder of Exemplified Compound I-1. The melting point was determined to be 171-173 ° C according to the Japanese Pharmacopoeia melting point measuring method. Since the elemental analysis values also agreed well with the calculated values, the structure of the exemplified compound H-1 was confirmed.

C H N calculated value 58.18% 4.48% 2.83% measured value 57.97% 4.55% 2.78% Exemplified compound represented by general formula [J]:

[0115]

[Chemical formula 63]

[0116]

[Chemical 64]

[0117]

[Chemical 65]

[0118]

[Chemical formula 66]

[0119]

[Chemical formula 67]

[0120]

[Chemical 68]

Synthesis example

[0122]

[Chemical 69]

Exemplified Compound J-1 was synthesized according to the above synthetic route. Compound 3 was synthesized according to a conventional method using 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) as a starting material.

10 g of Compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 9-aminophenanthrene 4 (manufactured by Aldrich Co.) and 100 ml of ODB were added, and an ester tube and a thermometer were attached and heated for 50 hours. Refluxed. After allowing to cool, the solid is removed by suction filtration and washed well with ethyl acetate. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column.
The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to give 9.3 g (yield 64%) of Exemplified Compound II-1 dark red crystals. The melting point was 193-194 ° C. as measured by the Japanese Pharmacopoeia melting point measuring method. The structure of Exemplified Compound J-1 was confirmed because the elemental analysis values also agreed well with the calculated values.

C H N calculated value 64.41% 2.52% 2.50% Actual value 64.32% 2.57% 2.45% Exemplary compound represented by the general formula [K]:

[0126]

[Chemical 70]

[0127]

[Chemical 71]

[0128]

[Chemical 72]

[0129]

[Chemical formula 73]

Synthesis example

[0131]

[Chemical 74]

Exemplified Compound K-1 was synthesized according to the above synthetic route. 2,4-bis (trifluoromethyl) bromobenzene 1 (manufactured by Aldrich) was used as a starting material, and compound 3 was used according to a known method (J. Chem, Soc, 1071-6 (1954)).
Was synthesized.

10 g of Compound 3 was placed in a 100 ml four-headed flask, 20 g of zinc chloride, 5 g of 1-amino-5,6,7,8-tetrahydronaphthalene 4 (manufactured by Aldrich) and 100 ml of ODB were added, and the ester tube and the temperature were adjusted. A meter was turned on and the mixture was heated under reflux for 50 hours. After cooling, the solid is removed by suction filtration and washed well with ethyl acetate and chloroform. The solvent of the mother liquor was distilled off under reduced pressure, and the residue was applied to a silica gel column. The toluene: n-hexane = 1: 1 eluate was crystallized from n-hexane to obtain 7.5 g (yield 55%) of a red powder of Exemplified Compound III-1.
Melting point was measured according to the Japanese Pharmacopoeia melting point measurement method 187-1
It was 88 ° C.

Since the elemental analysis values were in good agreement with the calculated values, the structure of Exemplified Compound K-1 was confirmed.

C H N calculated value 60.83% 3.14% 2.73% Actual value 60.68% 3.25% 2.70% Exemplified compound represented by the general formula [L]: Exemplified compound

[0136]

[Chemical 75]

[0137]

[Chemical 76]

[0138]

[Chemical 77]

[0139]

[Chemical 78]

[0140]

[Chemical 79]

[0141]

[Chemical 80]

[0142]

[Chemical 81]

[0143]

[Chemical formula 82]

[0144]

[Chemical 83]

[0145]

[Chemical 84]

[0146]

[Chemical 85]

[0147]

[Chemical 86]

[0148]

[Chemical 87]

Synthesis example

[0150]

[Chemical 88]

Exemplified Compound L-1 was synthesized according to the above synthetic route. Using 2,4-bis (trifluoromethyl) bromobenzene 1 as a starting material, a known method (J. Chem, Soc, 10
71 to 6 (1954)), compound 3 was synthesized.

CompoundThree Put 10g into a 100ml four-headed flask
20 g of zinc chloride and 5-amino-1-ethylpyrazoleFour
Add 5g (made by Aldrich) and 100ml ODB,
A tellurium tube and a thermometer were attached, and the mixture was heated under reflux for 40 hours. After cooling
The solid is filtered off with suction and rinsed well with DMSO. Mother liquor
The solvent was distilled off under reduced pressure and the residue was applied to a silica gel column.
did. Toluene: n-hexane = 9: 1 eluate,
9.3 g of red crystal of Exemplified Compound IV-1
(Yield 75%) was obtained. Melting point is according to Japanese Pharmacopoeia Melting Point Measurement Method
The measurement result was 168 to 170 ° C. Calculate elemental analysis values
Since the values were in good agreement, the structure of Exemplified Compound L-1 was
confirmed.

C H N calculated value 52.84% 2.53% 8.80% Actual value 52.81% 2.55% 8.77% In the electrophotographic photosensitive member of the present invention, examples of the conductive support include metal pipes, metal plates, metal sheets, and metal foils. ,
A conductive polymer film, a polymer film provided with a vapor deposition layer of a metal such as Al, a polymer film coated with a metal oxide, a quaternary ammonium salt, or the like, or paper is used.

In the electrophotographic photosensitive member of the present invention, the photosensitive layer is provided on the conductive support, but the photosensitive layer may have a single layer structure, or a laminated structure in which the charge generation layer and the charge transport layer are functionally separated. It may be one. An adhesive layer may be provided between the conductive support and the photosensitive layer.

In the photoreceptor of the present invention, as shown in FIGS. 1 (1) to 1 (4), an adhesive layer 5 is optionally provided on a conductive support 1, a photosensitive layer 6 is provided thereon, and further, an adhesive layer 5 is provided thereon. A protective layer 4 containing the electron-accepting substance according to the present invention is provided on the top. FIG. 1 (1) shows a direct P-type CTM on the conductive support 1.
CTL3 whose main component is CGL and CGL whose main component is CGM
2 is laminated in this order to form a photosensitive layer 6, on which a protective layer 4 containing the electron-accepting substance is provided.

FIG. 1B shows a structure in which an adhesive layer 5 is provided between the support 1 and the CTL 3 of the photoconductor of FIG. 1A.
FIG. 1 (3) shows the CGM in the CGL2 of the photoconductor of FIG. 1 (2).
Together with an appropriate amount of P-type or N-type CTM. 1 (4) has a structure in which a single-layer photosensitive layer in which CGM and P-type CTM coexist is provided in place of the double-layer photosensitive layer 6 in FIG. 1 (2).

The adhesive layer is formed of resin alone, coated with a dispersion of a low resistance compound such as tin oxide, indium oxide and titanium oxide in resin, aluminum oxide, zinc oxide, silicon oxide, etc. The vapor deposition film of The resin used for the adhesive layer is not particularly limited, and examples thereof include vinylidene chloride-vinyl chloride copolymer, water-soluble polyvinyl butyral resin, alcohol-soluble polyamide resin, vinyl acetate resin, polyvinyl alcohol, nitrocellulose, and polyimide resin. The thickness of the adhesive layer is 0.
The thickness is from 01 to 10 μm, preferably from 0.01 to 1 μm.

It is formed by the following method according to the characteristics of CTM and CGM forming the photosensitive layer 6.

(1) Vapor deposition method (2) Coating method a) Method of applying a solution coating in which CGM and CTM are dissolved in a suitable solvent b) CGM and CTM are finely dispersed in a dispersion medium by a ball mill, homomixer or the like. A method of applying a dispersion liquid coating obtained by making it into particles and optionally mixing and dispersing it with a binder. The vapor deposition method includes a vacuum deposition method, a sputtering method, an ion plating method, a CVD method and the like. Further, as a coating method, a suitable method is selected according to the physical properties of the coating such as a dipping method, a spray method, an air doctor method, a doctor blade method, a reverse roll method and a bar coat method.

In the two-layered photoreceptor of FIGS. 1 (1) to 1 (3), a P-type CTM is usually used to form CTL3.
Is dissolved in an organic solvent at a mixing ratio of 1: 100 to 100 to 1, preferably 1:20 to 20: 1 together with a binder resin, and the obtained coating solution is dried to a film thickness of 2 to 100 μm, preferably 5 to 50 μm.
Is applied and processed.

The P-type CTM is not particularly limited, and examples thereof include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidazolone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl. Compounds, hydrazone compounds, pyrazoline derivatives, oxazolone derivatives, benzothiazole derivatives,
It may be a benzofuran derivative, an acridine derivative, a phenazine derivative, an aminostilbene derivative, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene or the like.

Among them, for example, styryl compounds, hydrazone compounds, amine derivatives described in JP-A-62-157047, and Japanese Patent Application Nos. 4-55243, 4-55244 and 4-55.
Distyryl compounds described in each specification such as No. 245 are preferably used.

Examples of the binder resin used in the CTL3 include acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, vinyltoluene-styrene copolymer, styrene-modified alkyd resin, silicone-modified alkyd resin, soybean oil-modified alkyd. resin,
Vinylidene chloride-vinyl chloride resin, polyvinyl butyral, nitrated polystyrene, polymethylstyrene, polyisoprene, polyester, phenol resin, ketone resin, polyamide, polycarbonate, polythiocarbonate, polyamylate, polyhaloacrylate, vinyl acetate resin, Examples thereof include polystyrene, polyallyl ether, polyvinyl acrylate, polysulfone, polymethacrylate and the like. Among them, biphenyl Z type polycarbonate is particularly preferable.

Next, in order to form the CGL2 on the CTL3 in the two-layered photoreceptor of FIGS. 1 (1) to (3),
The ratio of CGM binder resin / CGM in the solution in which the binder resin is dissolved in an organic solvent is 0 to 10, preferably 0.1.
~ 2 to mix and stir to disperse into fine particles with an average particle size of 1 μm or less, and apply a coating solution consisting of the resulting dispersion to a dry film thickness of 0.01 to 10 μm, preferably 0.05 to 2 μm Obtained by processing.

In the two-layer photosensitive member of FIG. 1 (3), the N-type CTM or the P-type CTM is contained in CGL2 in an amount of 1 to 200 wt%, preferably 5 to 100 wt% with respect to the binder resin.
% Contained. Here, as the N-type CTM contained in CGL2 together with CGM, the electron-accepting substances represented by the above general formulas [A] to [L] according to the present invention are preferable, but other examples are Japanese Patent Application No. 3-3841. It may be an N-type CTM described in the specification.

Next, in order to form the photosensitive layer 6 in the photoreceptor of FIG. 4 in which the photosensitive layer 6 has a single layer structure, in the solution obtained by dissolving the above-mentioned P-type CTM together with the binder resin in the organic solvent. A coating solution of CGM dispersed in
˜50 μm, preferably 10 to 30 μm.

In this case, the ratio of binder resin / CGM is 0.05 to 20, preferably 0.1 to 5, and CTM is 1 to 200 wt%, preferably 5 to the binder resin.
~ 100wt%

The CGL2 may be formed by vapor deposition, and is usually formed by coating as described above.

The CGM contained in the CGL 2 and the photosensitive layer 6 of (4) in FIGS. 1 (1) to 1 (3) is Te-S.
Inorganic semiconductors such as e, organic semiconductors such as polyvinylcarbazole, bisazo compounds, trisazo compounds, metal-free phthalocyanine compounds, metal phthalocyanine compounds, pyrylium compounds, squarylium compounds, cyanine compounds, perylene compounds, many Organic pigments such as ring quinone compounds can be used. Among them, a preferable charge generating substance is, for example, 27.2 ° in JP-A-64-17066.
Y-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 2, and A-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 26.3 ° in JP-A-62-67094,
61-239248, B-type titanyl phthalocyanine pigment having an X-ray diffraction peak at 28.7 °, metal-free phthalocyanine pigment of JP-B-49-4338, copper phthalocyanine pigment of JP-A-57-163239, JP-A-57-148747. Vanadyl phthalocyanine pigment, JP-A-49-128734, perylene pigment, JP-A-4
There are condensed polycyclic pigments of No. 7-18544 and bisazo pigments of JP-A No. 1-150145. As the binder resin, polystyrene, silicone resin, polycarbonate resin, acrylic resin, methacrylic resin, polyester, vinyl polymer, cellulose resin, butyral resin, silicone modified butyral resin, alkyd resin, etc. can be used.

Next, the protective layer 4 provided on the photosensitive layer 6 of CGL 2 or (4) shown in FIGS. 1 (1) to 1 (3) is a binder resin and 0.1 to 200 wt% of the present invention with respect to the binder resin. It is formed by applying a coating solution containing the above-mentioned electron-accepting substance to a dry film thickness of 0.1 to 20 μm, preferably 1 to 5 μm.

The binder resin contained in the protective layer is, for example, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, butyral resin, polycarbonate resin, silicone resin or copolymer resin thereof. , For example vinyl chloride
-Vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, thermoplastic resin such as poly-N-vinylcarbazole are used. Further, by mixing with a thermoplastic resin or independently, for example, thermosetting acrylic resin, silicone resin, epoxy resin, urethane resin, urea resin,
Phenolic resin, polyester resin, alkyd resin,
A light or thermosetting resin such as a melamine resin, a photocurable / cinnamic acid resin, or a copolymerization or cocondensation resin thereof can also be used.

In addition to the electron-accepting substance, the protective layer may optionally contain an ultraviolet absorber or an antioxidant for the purpose of protecting CGM in CGL.

[0173]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto.

[Preparation of Photoreceptor] If necessary, an intermediate layer composed of a thin layer of an alcohol-soluble polyamide resin is provided on an aluminum tube, and various laminated and single-layer type photosensitive layers are provided on the intermediate layer. A protective layer containing an electron-accepting substance according to the present invention and an electron-accepting substance for comparison was provided on the photosensitive layer to obtain 40 kinds of photoreceptors (photoreceptors 1 to 40). Also above 40
A method of making various types of photoreceptors and a summary thereof (Tables 1 to 4) are shown below.

The laminated type includes a tentative name X type and a Z type.
The X type is a photosensitive layer in which CTL, CGL and a protective layer are laminated in this order on a substrate, and the Z type is a photosensitive layer containing CTM in the CGL of the X type photosensitive layer. The X-type photosensitive layer further includes X-type-1, X-type-2, X-type-3, X-type-4 and X-type.
Five photosensitive layers were set based on -5 different reference formulations.

The single layer type is tentatively called Y type, and is a photosensitive layer having a single layer structure composed of a layer containing both CGM and CTM on the substrate.

<Preparation of Photoreceptor 1 (X-type-1)> Copolymer nylon resin "CM-8000" (manufactured by Toray Industries) in methanol / 1-
0.15 μm on the PET base using butanol solution
Was provided. Next, a CTM with the following structure (CTM
1) 75 parts, polycarbonate resin "Panlite TS205
0 "(manufactured by Teijin Kasei) 100 parts, antioxidant" IRGANO
8 parts of "X1010" (manufactured by Ciba Geigy) and a small amount of silicon oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.)
A solution dissolved in 70 parts was applied by a dip coating method and dried to form a CTL having a film thickness of 25 μm.

Next, CGM (CGM1) 5 having the following structure
Part, 1 part of polyvinyl butyral resin "ESREC BL-S" (manufactured by Sekisui Chemical Co., Ltd.) as a binder resin is MEK
It was dispersed together with 200 parts of (methyl ethyl ketone) using a sand mill, coated using a circular slide hopper coating machine, and dried to form CGL having a film thickness of 0.3 μm. Further, on the CGL, 15 parts of the exemplified compound (A-1) and 100 parts of a silicone hard coating agent "KT-85" (manufactured by Shin-Etsu Chemical Co., Ltd.) were added.
The coating solution thus obtained was dissolved in 100 parts of F and was coated and cured using a circular slide hopper to form a surface protective layer of 3 μm, whereby a photoreceptor 1 having a laminated structure was obtained.

<Preparation of Photoreceptors 2 to 6 (X-type-1)> Exemplified compounds (B-2), (C-2), in place of the exemplified compound (A-1) in the protective layer of the photoreceptor 1. (D-3), (E-1)
And (F-5) were used in the same manner as in the photoconductor 1 to obtain a photoconductor 2, a photoconductor 3, a photoconductor 4, a photoconductor 5, and a photoconductor 6 having a laminated structure.

<Preparation of Photoreceptor 7 (X-Type-2)> 75 parts of CTM (CTM2) having the following structure, 100 parts of polycarbonate resin "UPILON Z300" (viscosity average molecular weight 30,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester resin "Byron 200"
(Toyobo Co., Ltd.) 10 parts, antioxidant "Sanol LS-262"
6 "(manufactured by Sankyosha) and a small amount of silicone oil" KF- "
A solution obtained by dissolving 54 "(manufactured by Shin-Etsu Chemical Co., Ltd.) in 500 parts of dichloromethane was applied onto an aluminum drum by a dip coating method, and after drying, a CTL having a film thickness of 25 μm was formed.

Next, CGM (CGM2) 2.5 having the following structure
Parts, 1 part of polyvinyl butyral resin "ESREC BX-1" (manufactured by Sekisui Chemical Co., Ltd.) as a binder resin
After dispersing with a sand mill together with 143 parts of K (methyl isopropyl ketone), it was coated using a circular slide hopper coater and dried to form a CGL having a film thickness of 0.5 μm. Further, on the CGL, 15 parts of the exemplified compound (G-1) and a silicone hard coat agent "KP-85" (manufactured by Shin-Etsu Chemical Co., Ltd.) 100
Part was dissolved in 100 parts of THF, and the obtained coating solution was applied and cured using a circular slide hopper to form a surface protection layer of 3 μm, and a photoconductor 7 having a laminated structure was obtained.

<Preparation of Photoreceptors 8 to 12 (X-Type-2)> In place of the exemplified compound (G-1) in the protective layer of the photoreceptor 7, exemplified compounds (H-3) and (J-4). , (K-3), (L-
Photoconductor 8, photoconductor 9, photoconductor 10, photoconductor 11, photoconductor 11 and photoconductor 12 having a laminated structure were obtained in the same manner as photoconductor 7 except that 1) and (A-3) were used.

<Preparation of Photoreceptor 13 (X-type-3)> 13 parts of CTM (CTM3) having the following structure and 20 parts of polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.), polyester resin "Byron 200"
(Toyobo Co., Ltd.) A solution prepared by dissolving 2 parts in 100 parts of 1,2-dichloroethane was applied on an aluminum drum by a dip coating method and dried, and then a CTL having a film thickness of 25 μm was formed. Next, 2 parts of CGM (CGM3) having the following structure, and polyvinyl butyral resin "ESREC BM-" as a binder resin
S ”(manufactured by Sekisui Chemical Co., Ltd.) was dispersed with 85 parts of MEK / cyclohexanone (= 4/1) using a sand mill, and then coated using a circular slide hopper coater and dried to give a film thickness of 0.7 μm. CGL was formed. Furthermore, 6 parts of the exemplified compound (B-8) and 10 parts of a polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of dichloromethane on the CGL to obtain a coating solution. After coating and drying using a circular slide hopper, surface protection having a film thickness of 5 μm was formed to obtain a photoconductor 13 having a laminated structure.

<Preparation of Photoreceptors 14 to 16 (X-Type-3)> Instead of the exemplified compound (B-8) in the protective layer of the photoreceptor 13, (C-
6), (D-7) and (E-8) except that a photoconductor 13 is used.
Photoreceptor 14, photoreceptor 15 and photoreceptor having a laminated structure similar to
Got 16.

<Preparation of Photoreceptor 17 (X-Type-4)> An intermediate layer made of polyamide resin "X-1874M" (manufactured by Daicel Hüls) having a thickness of 0.3 μm is provided on an aluminum tube, and an intermediate layer is provided thereon. 11 parts of CTM (CTM4) having the following structure and polycarbonate resin “UPILON Z300” (viscosity average molecular weight 30,00
0) 15 parts (manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 100 parts of dichloromethane to form a CTL having a film thickness of 25 μm. Next, 2 parts of the following CGM (CGM3), 0.2 part of CGM2,
As a binder resin, 1 part of polyvinyl butyral resin "ESREC BH-S" (manufactured by Sekisui Chemical Co., Ltd.) was dispersed together with 85 parts of MEK using a sand mill and then applied using a spray applicator to form a CGL having a film thickness of 0.5 μm. . Further, 15 parts of the exemplified compound (F-9) was dissolved in 100 parts of silicon hard coating agent "KP-85" and 100 parts of MEK on the CGL, and the obtained coating solution was applied using a spray coater, and after curing. A 2 μm surface protective layer is formed to form a laminated photoreceptor 1.
Got 7.

<Preparation of Photoreceptors 18 and 19 (X-type-4)> Exemplified compounds (G-5) and (H-10) were used in place of the exemplified compound (F-7) in the protective layer of the photoreceptor 17. Photoconductor 17
In the same manner as described above, a photosensitive member 18 and a photosensitive member 19 having a laminated structure were obtained.

[0187]

[Chemical 89]

[0188]

[Chemical 90]

<Preparation of Photoreceptor 20 (X-type-5)> Copolymer nylon resin "CM-8000" (manufactured by Toray Industries) in methanol / 1-
A 0.2 μm intermediate layer was provided on an aluminum drum substrate using butanol solution. Next, a solution prepared by dissolving 13 parts of the CTM (CTM2) and 20 parts of a polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 100 parts of 1,2-dichloroethane was immersed in an aluminum drum. After coating and drying by the coating method, C with a film thickness of 25 μm
TL was formed. Next, CGM (CGM5) having the following structure
2 parts, 1 part of cellulose-modified silicone resin "KR-5240" (manufactured by Shin-Etsu Chemical Co., Ltd.) as a binder resin, and 1 part of t-butyl acetate
After being dispersed together with 00 parts using a sand mill, it was coated using a circular slide hopper and dried to form a CGL having a film thickness of 0.2 μm. Further, 6 parts of the exemplified compound (J-9) and 10 parts of a polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of dichloromethane on the CGL to obtain a coating solution. After coating and drying using a circular slide hopper, a surface protective layer having a film thickness of 5 μm was formed to obtain a photoconductor 20 having a laminated structure.

[0190]

[Chemical Formula 91]

<Preparation of Photoreceptors 21 and 22 (X-type-5)> Exemplified compounds (K-12) and (L-15) were used in place of the exemplified compound (J-9) in the protective layer of the photoreceptor 20. Other than used, photoconductor 20
Photosensitive members 21 and 22 having a laminated structure were obtained in the same manner as in.

<Preparation of Photoreceptor 23 (Y Type)> CGM
(CGM3) 10 parts, CTM (CTM2) 15 parts, polycarbonate resin "UPILON Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) 20 parts were dispersed together with 45 parts of 1,2-dichloroethane using a sand mill. Then, after coating by a dip coating method and drying, a photosensitive layer having a film thickness of 25 μm was obtained.
Further, 15 parts of Exemplified Compound (A-1) was dissolved in 100 parts of silicon hard coating agent "KP-85" and 100 parts of MEK on the photosensitive layer, and the obtained coating solution was applied and cured using a spray coating machine. After that, a surface protective layer having a thickness of 2 μm was formed to obtain a single-layer photosensitive member 23.

<Preparation of Photoreceptor 24 (Y Type)> In place of the exemplified compound (A-1) in the protective layer of the photoreceptor 23, the exemplified compound (A
A single-layer photosensitive member 24 was obtained in the same manner as the photosensitive member 23 except that (3) was used.

<Production of Photoreceptors 25 and 26 (Y Type)> Photoreceptor
CTM3 in the photosensitive layer of 23 was used instead of CTM3, and the exemplary compound (E- was used instead of the exemplary compound (A-1) in the protective layer.
30) and (H-4) were used, and single-layer photosensitive members 25 and 26 were obtained in the same manner as the photosensitive member 23.

<Preparation of Photoreceptor 27 (Y Type)> Exemplified compound (A-1) was used in place of CTM2 in the photosensitive layer of photoreceptor 23, and replaced with Exemplified compound (A-1) in the protective layer. A single-layer photoreceptor 27 was obtained in the same manner as the photoreceptor 23 except that the exemplified compound (CT-17) was used.

<Production of Photoreceptor 28 (Z Type)> CTM
(CTM4) 7 parts, Polycarbonate resin "Panlite TS2050" (manufactured by Teijin Chemicals Co., Ltd.), and a small amount of silicon oil "KF-54" (manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 67 parts dichloromethane. After coating by a coating method and drying, a CTL having a film thickness of 25 μm was formed. Next, 10 parts of the CGM (CGM3) and the CTM (CTM3) 15
Parts, 20 parts of polycarbonate resin "Iupilon Z200" (viscosity average molecular weight 20,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 35 parts of 1,2-dichloroethane were dispersed in a sand mill, and then coated using a circular slide hopper and dried. After that, a CGL having a film thickness of 5 μm was formed. Further, 6 parts of Exemplified Compound (A-1) and 10 parts of polycarbonate resin "Iupilon Z800" (viscosity average molecular weight 80,000) (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 100 parts of 1,2-dichloroethane on the CGL to obtain the compound. The coating solution was applied using a circular slide hopper and dried, and then a surface protective layer having a film thickness of 5 μm was formed to obtain a photoreceptor 28 having a multilayer structure.

<Preparation of Photoreceptors 29, 30 and 31 (Z Type)> Exemplified compounds (C-14), (E-30) and (E-30) in place of the exemplified compound (A-1) in the protective layer of the photoreceptor 28. Photosensitive members 29, 30 having a multi-layer structure in the same manner as the photosensitive member 28 except that (H-2) is used, and
Got 31

<Preparation of Comparative Photoreceptors 32 and 32 (X-Type-1)> Exemplified Compounds (M-1) and (M-2) instead of Exemplified Compound (A-1) in the protective layer of Photoreceptor 1. ) Was used in the same manner as the photoconductor 1 to obtain photoconductors 32 and 33 having a laminated structure.

<Preparation of Comparative Photosensitive Members 34 and 35 (X-Type-2)> Except that the exemplified compound (M-1) in the protective layer of the photosensitive member 7 was used in place of the exemplified compound (M-1). A photoconductor 35 having a laminated structure was obtained in the same manner as the photoconductor 7.

<Preparation of Comparative Photoreceptor 36 (X-Type-3)> Except that Exemplified Compound (M-1) was used instead of Exemplified Compound (B-8) in the protective layer of Photoreceptor 13 A photoconductor 36 having a laminated structure was obtained in the same manner as 13.

<Preparation of Comparative Photoreceptor 37 (Y Type)> Photoreceptor
A photoreceptor 37 having a single-layer structure was obtained in the same manner as the photoreceptor 23 except that the exemplified compound (M-1) was used in place of the exemplified compound (A-1) in the protective layer of 23.

<Preparation of Comparative Photosensitive Member 38 (Y Type)> Photosensitive Member
A photoreceptor 38 having a single layer structure was obtained in the same manner as the photoreceptor 25 except that the exemplified compound (M-2) was used in place of the exemplified compound (E-30) in the protective layer of No. 25.

<Preparation of Comparative Photoreceptors 39 and 40 (Z Type)>
Photoreceptor except that Exemplified Compounds (M-1) and (M-2) are used instead of Exemplified Compound (A-1) in the protective layer of Photoreceptor 28.
Photoconductors 39 and 40 having a laminated structure were obtained in the same manner as in 28.

The 40 types of photoconductors are summarized in Tables 1 to 4 below.

[0205]

[Table 1]

[0206]

[Table 2]

[0207]

[Table 3]

[0208]

[Table 4]

[Image Test and Electrostatic Property Test] Konica
U-BIX3035 manufactured by Co., Ltd. was modified into a positive charging system, and the above 40 kinds of photoconductors were sequentially mounted on the modified machine. RH 60%, 20 ° C
Performed a continuous copy test over 10,000 times in the atmosphere of
Image quality evaluation and electrostatic characteristic test centering on the fog density at the initial stage and at the time of copying 10,000 times were performed. In order to perform the image test and the electrostatic characteristic test, first, the developing device of the copying machine is removed before the start of copying, a potential measuring probe is arranged instead, and the copying machine is driven to drive the black paper potential V _b , The blank sheet potential V _w and the residual potential V _r are measured. Then, instead of the probe, a developing device was attached and continuous image formation was carried out 10,000 times. After completion of copying, the potential measuring probe was placed at the developing device position in the same manner as in the initial stage. V _b , V _w and V
_{The r} was measured and the results are shown in Table 5. Also, the fog density of the image of the initial copy and the 10,000th copy is measured by a densitometer "Macbeth RD".
918 "(manufactured by Eastman Kodak Company), and evaluated by the" ○ "and" × "methods according to the following evaluation criteria,
The results are shown in Table 5.

Evaluation criteria: Fogging density less than 0.005 ◎ 0.005 to 0.008 ○ 0.009 to 0.012 △ 0.013 or more × However, the above fog density (A) is obtained by measuring with the densitometer from the measured density (B) to the white paper reflection density (C). ) Is the value subtracted.

That is, the obtained fog density A = BC.

[0212]

[Table 5]

As shown in Table 5, the photoconductors of the examples have high sensitivity because the white paper potential V _w is low with respect to the black paper potential V _b at the time of positive charging, even though the protective layer is provided. After 10,000 times of image formation, the residual potential is small and the high image quality without fogging is stably obtained from the beginning. On the other hand, the photoconductor of the comparative example has a large blank sheet potential V _w , and the decrease in sensitivity is noticeable. It can be seen that there is a lot of fog and the image quality is unclear due to the remarkable rise, which is not practical.

[0214]

According to the photoreceptor of the present invention, a protective layer containing an electron-accepting substance peculiar to the present invention is provided on the surface of the photoreceptor for positive charging, so that deterioration due to repeated charging and exposure and mechanical Deterioration due to abrasion is prevented, high sensitivity characteristics are provided, and there is an effect such that a clear image can be stably obtained without fog over a long period of time without an increase in residual potential during repeated image formation. To be done.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a layer structure of various photoconductors included in the present invention.

[Explanation of symbols]

 1 Conductive Support 2 Charge Generation Layer (CGL) 3 Charge Transport Layer (CTL) 4 Protective Layer 5 Adhesive Layer 6 Photosensitive Layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naohiro Hirose, Konica Stock Company, Sakura City, Hino City, Tokyo (72) Inventor Tomomi Oshiba, Konica Stock Company, Sakura City, Hino City, Tokyo

Claims (55)

[Claims] 1. A protective layer comprising a photosensitive layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron accepting substance represented by the general formula [A]. An electrophotographic photoreceptor having a layer. [Chemical 1] [In the formula, R _A is a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, a COOR _A ′ group, an OCOR _A ′ group, a CON
H ₂ group, CONHR _A ′ group, CON (R _A ′) ₂ group, COR
_A 'group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, R _A' is an optionally substituted alkyl group, an aryl group or an aralkyl group Represents l, m and n
Each represent 0 or a positive integer, and when 1 is 0, m is 2
The above integers are represented, and when l is an integer of 1 or more, m represents 0 or a positive integer. The plural groups represented by R _A may be the same or different. ] 2. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. The electrophotographic photosensitive member according to claim 1, further comprising a protective layer. 3. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 4. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support,
The electrophotographic photoreceptor according to claim 1, wherein the protective layer is provided on the photosensitive layer. 5. The electron-accepting substance represented by the general formula [A] is a compound represented by the following general formula [a], claim 1, claim 2, claim 3 or Claim 4
The electrophotographic photosensitive member according to any one of 1. [Chemical 2] [In the formula, R _1A and R _2A represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as those in the general formula [A], and p is 0 or a positive integer. Represents ] 6. A protective layer comprising a photosensitive layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron-accepting substance represented by the general formula [B]. An electrophotographic photoreceptor having a layer. [Chemical 3] [In the formula, Y _B represents a cyano group or a CF ₃ group, and R _B represents a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, COO.
R _B ′ group, OCOR _B ′ group, CONH ₂ group, CONHR _B ′
Group, CON (R _B ′) ₂ group, COR _B ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, and R _B ′ has a substituent group. Represents an alkyl group, an aryl group or an aralkyl group which may be present. l, m and n each represent an integer of 1 or more. The plural groups of Y _B and R _B may be the same or different. ] 7. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. The electrophotographic photosensitive member according to claim 6, wherein a protective layer is provided. 8. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. The electrophotographic photosensitive member according to claim 6, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 9. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support,
The electrophotographic photoreceptor according to claim 1, wherein the protective layer is provided on the photosensitive layer. 10. The electron accepting substance represented by the general formula [B] is a compound represented by the following general formula [b], claim 6, claim 7, claim 8 or The electrophotographic photosensitive member according to claim 9. [Chemical 4] [Wherein R _1B and R _2B represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as those in the general formula [B], and p represents 0 or a positive integer. Represent ] 11. A protective layer containing a charge generating substance and a P-type charge transporting substance on a conductive support, and the photosensitive layer containing an electron accepting substance represented by the general formula [C]. An electrophotographic photoreceptor having a layer. [Chemical 5] [Wherein X _C is a COOR _C ′ group, an OCOR _C ′ group, a CON
H ₂ group, CONHR _C ′ group, CON (R _C ′) ₂ group, COR
Represents a _C ′ group or a CHO group, and Y _C represents a halogen atom, a cyano group, a nitro group, a CF ₃ group, a COOH group, a SO ₂ NH ₂ group,
Represents a SO ₂ R _C ′ group or a SOR _C ′ group, wherein R _C is a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, a COOR _C ′
Group, OCOR _C ′ group, CONH ₂ group, CONHR _C ′ group,
A CON (R _C ′) ₂ group, a COR _C ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R _C ′ has a substituent Represents an alkyl group, an aryl group or an aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X _C , Y _C and R _C may be the same or different. ] 12. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 12. The electrophotographic photosensitive member according to claim 11, which is provided with a protective layer. 13. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 12. The electrophotographic photosensitive member according to claim 11, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 14. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 11. The electrophotographic photosensitive member according to item 11. 15. The electron accepting substance represented by the general formula [C] is a compound represented by the following general formula [c], 11, 12, 13 or Claim
The electrophotographic photosensitive member according to any one of 14. [Chemical 6] [In the formula, X _C and Y _C have the same meanings as those in the general formula [C],
R _1C and R _2C represent a halogen atom, a cyano group or an alkyl group which may have a substituent. l and m have the same meaning as in the general formula [C], and p represents 0 or a positive integer. ] 16. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [D]. An electrophotographic photoreceptor having a layer. [Chemical 7] [In the formula, X _D represents a COOH group, SO ₂ NH ₂ group, SOR _D ′ group or SO ₂ R _D ′ group, Y _D represents a halogen atom, a cyano group, a nitro group or a CF ₃ group, and R _D Is a halogen atom,
Hydroxy group, nitro group, CF ₃ group, COOR _D ′ group, O
COR _D ′ group, CONH ₂ group, CONHR _D ′ group, CON
(R _D ′) ₂ group, COR _D ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R _D ′ may have a substituent Represents a good alkyl group, aryl group or aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X _D , Y _D and R _D may be the same or different. ] 17. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is provided on the charge-generating layer. 17. The electrophotographic photosensitive member according to claim 16, further comprising a protective layer. 18. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 17. The electrophotographic photosensitive member according to claim 16, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 19. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 16. The electrophotographic photosensitive member according to item 16. 20. The electron accepting substance represented by the general formula [D] is a compound represented by the following general formula [d], 16, 17, 18 or Claim
The electrophotographic photosensitive member according to any one of 19. [Chemical 8] [In the formula, X _D and Y _D have the same _{meanings as those} in the general formula [D],
Each group of R _1D and R _2D represents a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meaning as in the general formula [D], and p is 0 or a positive integer. Represent ] 21. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [E] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 9] [Wherein X _E represents a halogen atom, Y _E represents a cyano group, a nitro group or a CF ₃ group, and R _E represents a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, a COOR _E ′ group, OCOR
_E 'group, CONH ₂ groups, CONHR _E' group, CON
(R _E ′) ₂ group, COR _E ′ group or an optionally substituted alkyl group, alkoxy group, aryl group, aralkyl group or alkylamino group, wherein R _E ′ may have a substituent Represents a good alkyl group, aryl group or aralkyl group. l and n represent an integer of 1 or more, m represents 0 or a positive integer, and l + m represents an integer of 2 or more. The plural groups of X _E , Y _E and R _E may be the same or different. ] 22. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 22. The electrophotographic photosensitive member according to claim 21, further comprising a protective layer. 23. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 23. The electrophotographic photosensitive member according to claim 22, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 24. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 23. The electrophotographic photoconductor of Item 23. 25. The electron-accepting substance represented by the general formula [E] is a compound represented by the following general formula [e], 21, 21, 23, or Claim
The electrophotographic photosensitive member according to any one of 24. [Chemical 10] [In the formula, X _E and Y _E have the same _{meanings as those} in the general formula [E],
R _1E and R _2E represent a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meanings as in the general formula [E], and p represents 0 or a positive integer. ] 26. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [F] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 11] [In the formula, X _F is a halogen atom, a cyano group, a nitro group, C
F ₃ group, COOH group, COOR _F ′ group, OCOR _F ′ group,
CONH ₂ group, CONHR _F ′ group, CON (R _F ′) ₂ group,
COR _F ′ group, SO ₂ NH ₂ group, SOR _F ′ group, SO ₂ R _F ′
Group or CHO group, Y _F represents an alkyl group which may have a substituent, an aryl group or an aralkyl group, and R _F represents a halogen atom, a hydroxy group, a nitro group, a CF ₃ group, C
OOR _F 'group, OCOR _F' group, CONH ₂ groups, CONH
Represents an R _F ′ group, a CON (R _F ′) ₂ group, a COR _F ′ group or an optionally substituted alkyl group, an alkoxy group, an aryl group, an aralkyl group or an alkylamino group, and R
_F'represents an alkyl group, an aryl group or an aralkyl group which may have a substituent. The plural groups of X _F , Y _F and R _F may be the same or different. ] 27. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 27. The electrophotographic photosensitive member according to claim 26, which is provided with a protective layer. 28. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 27. The electrophotographic photosensitive member according to claim 26, wherein the protective layer is provided on the charge generation layer. 29. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 26. The electrophotographic photoreceptor according to Item 26. 30. The electron accepting substance represented by the general formula [F] is a compound represented by the following general formula [f], 26, 27, 28 or Claim
The electrophotographic photosensitive member according to any one of 29. [Chemical 12] [In the formula, X _F and Y _F have the same _{meanings as those} in the general formula [F],
Each group of R _1F and R _2F represents a halogen atom, a cyano group or an alkyl group which may have a substituent, l and m have the same meaning as in the general formula [F], and p is 0 or a positive integer. Represent ] 31. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the photosensitive layer is protected by containing an electron accepting substance represented by the general formula [G]. An electrophotographic photoreceptor having a layer. [Chemical 13] [In the formula, Y _1G represents an alkyl group which may have a substituent, R _2G represents a halogen atom, a hydroxy group, a cyano group, a nitro group, an N (R _G ′) ₂ group, an OR _G ′ group, COOR _G'group ,
OCOR _G ′ group, COR _G ′ group, CONHR _G ′ group, CO
N (R _G ′) ₂ group, SOR _G ′ group, SO ₂ R _G ′ group or an optionally substituted aryl group or aralkyl group, and R _G ′ is an optionally substituted alkyl group Represents a group, an aryl group or an aralkyl group. l represents 0 or a positive integer, m represents an integer of 2 or more, and n represents an integer of 1 or more. The plurality of Y _1G and R _2G groups may be the same or different. ] 32. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is formed on the charge-generating layer. 32. The electrophotographic photosensitive member according to claim 31, which is provided with a protective layer. 33. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 33. The electrophotographic photosensitive member according to claim 32, wherein the protective layer is provided on the charge generation layer. 34. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 33. The electrophotographic photoconductor of Item 33. 35. The electron-accepting substance represented by the general formula [G] is a compound represented by the following general formula [g], 31, 32, 33 or Claim
The electrophotographic photosensitive member according to any one of 34. [Chemical 14] [Wherein Y _1G has the same meaning as in the general formula [G], and R ′ _2G represents a halogen atom, a cyano group, a nitro group, a COOR _G ′ group, O
Represents a COR _G ′ group, a COR _G ′ group or a CONHR _G ′ group. L'represents 0, m'represents an integer of 3 or more, n
And R _G ′ have the same meaning as in general formula [G]. ] 36. A photosensitive layer containing a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer containing an electron accepting substance represented by the general formula [H] is provided on the photosensitive layer. An electrophotographic photoreceptor having a layer. [Chemical 15] [Wherein, X _H is a hydroxy group, OR _H ′ group, N (R _H ′) ₂
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, and Y _H represents a halogen atom, a cyano group, a nitro group, a CF ₃ group, a COR _H ′ group, a COOR _H ′.
Group, OCOR _H ′ group, CONHR _H ′ group, CON
Represents a (R _H ′) ₂ group, a SOR _H ′ group or a SO ₂ R _H ′ group,
R _H represents an alkyl group or an aralkyl group which may have a substituent, and R _H ′ represents an alkyl group or an aryl group which may have a substituent. l represents 0 or a positive integer, m represents an integer of 2 or more, and l + m represents an integer of 2 to 8.
The plural groups of X _H , Y _H and R _H ′ may be the same or different. Further, when the substituent in the general formula [H] is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group may be linear, branched or cyclic and may be substituted. An alkyl group which may contain a saturated bond (eg, methylethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group). , Methoxyethyl group, phenoxyethyl group). When the substituent in the general formula [H] is an aryl group or includes an aryl group, the aryl group may be substituted unless otherwise specified, and may be a monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group,
p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3,4-dichlorophenyl group) To do. ] 37. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, a charge-generating layer containing a charge-generating substance is provided on the charge-transporting layer, and the charge-generating layer is provided on the charge-generating layer. 37. The electrophotographic photosensitive member according to claim 36, which is provided with a protective layer. 38. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 37. The electrophotographic photosensitive member according to claim 36, wherein the protective layer is provided on the charge generation layer. 39. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 36. The electrophotographic photoconductor of Item 36. 40. The electron-accepting substance represented by the general formula [H] is a compound represented by the following general formula [h], 36, 37, 38 or Claim
The electrophotographic photosensitive member according to any one of 39. [Chemical 16] Wherein, X _'H denotes the following lower alkyl group 5 carbon atoms, Y' _H represents a cyano group, CF ₃ group, COR _'H' group or COOR _'H' group, R _'H groups and R _'H' group represents a 5 or greater alkyl group carbon atoms. Further, m ′ represents an integer of 3 to 5, and l has the same meaning as in the general formula [H]. ] 41. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [J]. An electrophotographic photoreceptor having a layer. [Chemical 17] [Wherein, X _J is a hydroxy group, OR _J ′ group, N (R _J ′) ₂
A group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, wherein Y _J and R _F are halogen atoms,
Cyano group, nitro group, CF ₃ group, COOR _J ′ group, OCO
R _J ′ group, CONHR _J ′ group, SOR _J ′ group or SO
₂ represents an R _J ′ group, R _J ′ represents an optionally substituted alkyl group, an aryl group or an aralkyl group, and A represents an atomic group necessary for forming a condensed polycyclic aromatic carbocycle. Represent
l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plural groups of X _J , Y _J and R _F may be the same or different. When the substituent in the general formula [J] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. An alkyl group which is a ring and may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, Allyl group, oleyl group, benzyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [J] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and a monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3 ,
4-dichlorophenyl group) is meant. ] 42. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 42. The electrophotographic photosensitive member according to claim 41, which is provided with a protective layer. 43. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 43. The electrophotographic photosensitive member according to claim 42, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 44. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 43. The electrophotographic photosensitive member according to Item 43. 45. The electron-accepting substance represented by the general formula [J] is a compound represented by the following general formula [j], 41, 42, 43 or The electrophotographic photosensitive member according to claim 44. [Chemical 18] Wherein, X _'J represents a lower alkyl group having not more than 5 carbon atoms, Y' _J, each group R _'J represents a cyano group, CF ₃ group, CO
Represents R _'J' group or COOR _'J' group, R _'J' represents an 5 or greater alkyl group carbon atoms, A 'is a naphthalene,
It represents a hydrocarbon atom group necessary for forming an anthracene, phenanthrene or pyrene ring. l'and n'represent 0 or a positive integer, and m'represent an integer of 3 to 5. ] 46. A protective layer comprising, on a conductive support, a photosensitive layer containing a charge generating substance and a P-type charge transporting substance, and the photosensitive layer containing an electron accepting substance represented by the general formula [K]. An electrophotographic photoreceptor having a layer. [Chemical 19] [Wherein X _K is a hydroxy group, OR _K ′ group, N (R _K ′) ₂
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, wherein Y _K and R _K are halogen atoms,
Cyano group, nitro group, CF ₃ group, COR _K ′ group, COOR
'I represent a group, R _{K' K} 'groups, OCOR _K' groups, CONHR _K 'groups, SOR _K' groups or SO ₂ R _K represents an optionally substituted alkyl group, an aryl group or an aralkyl group , B
Represents a hydrocarbon atom group necessary for forming an aliphatic ring together with the carbon atom of the benzene ring. l, m and n represent 0 or a positive integer, n + m represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The plurality of R _K , Y _K , and R _K groups may be the same or different. When the substituent in the general formula [K] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. A ring, which may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group,
Pentyl group, 2-ethylhexyl group, dodecyl group, allyl group, oleyl group, benzyl group, hydroxyethyl group,
Methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [K] is an aryl group or contains an aryl group, the aryl group may be substituted unless otherwise specified, and the monocyclic or condensed ring aryl group (for example, Phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3 , 4-dichlorophenyl group). ] 47. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 47. The electrophotographic photosensitive member according to claim 46, which is provided with a protective layer. 48. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 47. The electrophotographic photosensitive member according to claim 46, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 49. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 46. The electrophotographic photoreceptor according to Item 46. 50. The electron-accepting substance represented by the general formula [K] is a compound represented by the following general formula [k], 46, 47, 48 or Claim
The electrophotographic photosensitive member according to any one of 49. [Chemical 20] [Wherein _X'K is a lower alkyl group having 5 or less carbon atoms,
Y _'K, R' each group a cyano group _K, CF ₃ group, COR _'K'
It represents a group or COOR _'K' group, R _'K' groups represents an alkyl group having at least 5 carbon atoms, B 'represents a hydrocarbon atomic group necessary to form an aliphatic ring of 5 or 6-membered . l'and n'represent 0 or 1, m'represents an integer from 3 to 5,
n '+ m' represents an integer of 3 or more. ] 51. A photosensitive layer containing a charge-generating substance and a P-type charge-transporting substance is provided on a conductive support, and the electron-accepting substance represented by the following general formula [L] is contained on the photosensitive layer. An electrophotographic photoreceptor comprising a protective layer. [Chemical 21] [Wherein X _L is a hydroxy group, OR _L ′ group, N (R _L ′) ₂
Represents a group or an alkyl group which may have a substituent, an aryl group or an aralkyl group, Y _L and R _L are halogen atoms,
Cyano group, nitro group, CF ₃ group, COR _L ′ group, COOR
_L 'represents a group, R _L' 'group, OCOR _L' groups, CONHR _L 'group, SOR _L' groups or SO ₂ R _L represents an optionally substituted alkyl group, an aryl group or an aralkyl group , D
Represents a group of non-metal atoms necessary for forming a heterocycle. l,
m and n represent 0 or a positive integer, m + n represents an integer of 2 or more, and l + m represents an integer of 2 to 8. The X _L,
The groups Y _L and R _L may be the same or different. When the substituent in the general formula [L] is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cross-linked alicyclic unless otherwise specified. A ring, which may be substituted or may contain an unsaturated bond (eg, methyl group, ethyl group, iso-propyl group, t-butyl group, pentyl group, 2-ethylhexyl group, dodecyl group) , Allyl group, oleyl group, benzyl group,
Hydroxyethyl group, methoxyethyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, norbornyl group). When the substituent in the general formula [L] is an aryl group or contains an aryl group,
Unless otherwise specified, the aryl group may be substituted and has a monocyclic or condensed ring aryl group (eg, phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, 4-methoxyphenyl group, Pentafluorophenyl group, p-hydroxyphenyl group, p-cyanophenyl group, p-methanesulfonamidophenyl group, 3,4-
Dichlorophenyl group). ] 52. A charge transporting layer containing a P-type charge transporting substance is provided on a conductive support, a charge generating layer containing a charge generating substance is provided on the charge transporting layer, and the charge generating layer is provided on the charge generating layer. 52. The electrophotographic photosensitive member according to claim 51, wherein a protective layer is provided. 53. A charge-transporting layer containing a P-type charge-transporting substance is provided on a conductive support, and a charge-generating layer containing a charge-generating substance and a P-type or N-type charge-transporting substance is provided on the charge-transporting layer. 52. The electrophotographic photosensitive member according to claim 51, wherein the electrophotographic photosensitive member is provided, and the protective layer is provided on the charge generation layer. 54. A photosensitive layer comprising a layer containing both a charge generating substance and a P-type charge transporting substance is provided on a conductive support, and the protective layer is provided on the photosensitive layer. Item 51. The electrophotographic photosensitive member according to item 51. 55. The electron-accepting substance represented by the general formula [L] is a compound represented by the following general formula [l], 51, 52, 53 or Claim
The electrophotographic photosensitive member according to any one of 54. [Chemical formula 22] Wherein, X _'L represents a lower alkyl group having not more than 5 carbon atoms, Y' _L, each group R _'L is a cyano group, CF ₃ group, CO
Represents R _'L' group or COOR _'L' group, R _'L' groups represents an alkyl group having at least 5 carbon atoms, D 'is O, N,
Non-metallic atomic group necessary for forming a 3- to 8-membered optionally substituted monocyclic or heterocyclic ring consisting of a condensed ring containing at least one heteroatom selected from S, P, Se and Te in the ring And the heterocycle is succinimide,
Maleimide, phthalimide, pyrrole, pyrazole, imidazole, selenazole, triazole, tetrazole, indole, pyridine, pyrimidine, morpholine,
Heterocycles such as triazine, phosphazene, benzimidazole, benzthiazole, benzthiadiazole, and imidazolopyrimidine are mentioned. Also preferably, D '
Represents an atomic group necessary for forming a heterocycle consisting of a 5- or 6-membered optionally substituted monocyclic or condensed ring containing at least one heteroatom selected from O, N and S in the ring. l'and n'represent 0 or 1, m'represents an integer of 3 to 5, and n '+ m' represents an integer of 3 or more. ]