JPH0643678A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body high in sensitivity and superior in durability by using a specified electric charge generating material, a specified charge transfer material, and a specified stabilizer. CONSTITUTION:This electrophotographic sensitive body uses the charge generating material of the bisazo pigment represented by formula I and the charge transfer material of the diamine type compound represented by formula II and the stabilizer represented by formula III. In formulae I-III, each of A<1> and A<2> is a coupler residue: R<1> is H, optionally substituted alkyl, such aryl, or such a heterocyclic group; n is 0 or 1; each of R<2>-R<7> is alkyl, alkoxy, halogen, aryl, nitro, cyano, or alkylamino; each of p and q is 0, 1, 2, or 3: each of k, l, m, and o is 0, 1, or 2; each of Y<1> and Y<2> is alkylene; each of R<20>-R<23> is 11, or alkyl; R<24> is H, aralkyl, car aryl; and r is an integer of 3-40.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member used in an image forming apparatus using an electrophotographic method such as an electrostatic copying machine and a laser beam printer.

[0002]

2. Description of the Related Art The electrophotographic method such as the Carlson process is a step of uniformly charging the surface of an electrophotographic photosensitive member by corona discharge, and exposing the charged surface of the electrophotographic photosensitive member to an electrostatic latent image on the surface. An exposure step of forming an image, a developing step of bringing a developer into contact with the formed electrostatic latent image, and developing the electrostatic latent image into a toner image by toner contained in the developer, and a toner image Transfer step of transferring the toner to paper, a fixing step of fixing the transferred toner image, and a transfer step,
And a cleaning step for removing the toner remaining on the photoconductor.

Recently, the electrophotographic photosensitive member used in the above-mentioned electrophotographic method is replaced with a main component containing an inorganic photoconductor such as selenium or cadmium sulfide, which is difficult to handle due to toxicity. Various so-called organic photoconductors using organic photoconductive compounds with low toxicity have been proposed. Such an organic photoreceptor has the advantages that it has good processability, is easy to manufacture, and has a high degree of freedom in functional design.

In such an organic photoreceptor, generally, a function-separated type photosensitive layer containing a charge generating material for generating charges by light irradiation and a charge transporting material for transporting the generated charges is often used. . As a charge generating material used in the above electrophotographic photoreceptor, Japanese Patent Application Laid-Open No. 1-2202757 discloses a specific bisazo pigment. This bisazo pigment is represented by the following general formula (1).

[0005]

[Chemical 7]

(In the formula, A ¹ and A ² are the same or different and each represents a coupler residue, and R ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. An alkyl group, an aryl group, The heterocyclic group may have a substituent, n is 0 or 1.) Such a bisazo pigment (1)
Has the advantages of being stable to heat and light, having high charge generation efficiency, high sensitivity, and excellent repeatability.

[0007]

By the way, in order to prepare a function-separated type organic photoreceptor using a charge generating material and a charge transporting material, sensitivity, potential holding property, potential stability,
A material with good matching that satisfies all electrophotographic characteristics such as residual potential must be selected. For example, no matter how much charge-generating material generates sufficient charge, satisfactory electrophotographic characteristics cannot be obtained unless it is combined with a charge-transporting material capable of efficiently injecting and transporting the charge. .

According to the above-mentioned JP-A-1-202757, the use of the bisazo pigment represented by the general formula (1) in combination with various charge transport materials (carrier transfer substances) results in heat and light. In contrast, it is disclosed that a stable photoconductor can be obtained. However, the bisazo pigment (1) disclosed in the above publication is a phthalocyanine-based or perylene-based pigment, a fluorenone-type bisazo pigment (JP-A-57-96345), which is a commonly used charge generating material, and a perinone skeleton. As compared with oxadiazole type azo pigments having a coupler with a light (Japanese Patent Laid-Open No. 59-229564) and the like, ozone and nitrogen oxides NOx generated in a copying machine, light and the like are more likely to cause oxidative deterioration, resulting in a photoreceptor. It has a drawback that it tends to cause deterioration of characteristics. It is presumed that the oxidative deterioration of the bisazo pigment (1) occurs because ozone or the like adsorbs to the azo group and decomposes the azo group.

Such oxidative deterioration is caused by the above bisazo pigment.
It is promoted when (1) is used in combination with a charge transport material which is an electron donating compound. This is because if the electron-donating compound has a strong basicity, the electron-donating compound coordinates with the azo group and increases the electron density of the azo group, which makes it more susceptible to attack by ozone and nitrogen oxides. To be

Therefore, it was not possible to obtain a photoreceptor having high sensitivity and repetitive characteristics without impairing the excellent characteristics of the bisazo pigment (1). The present invention has been made in view of the above circumstances, and the general formula
An object of the present invention is to provide a high-performance electrophotographic photoreceptor having high sensitivity and excellent durability by using the bisazo pigment represented by (1) as a charge generating material.

[0011]

Means and Actions for Solving the Problems As a result of intensive studies on the charge transport material used in combination with the bisazo pigment, the present inventors have shown that it is represented by the general formula (1), which is a charge generating material. Bisazo pigment and a general formula (2) which is a charge transport material:

[0012]

[Chemical 8]

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are an alkyl group, an alkoxyl group, a halogen atom, an aryl group, a nitro group, a cyano group or an alkylamino group. (P and q represent integers of 0 to 3, and k, l, m and o represent integers of 0 to 2.)
An electrophotographic photosensitive member provided with a photosensitive layer containing a diamine compound represented by on a conductive substrate is stable against ozone and nitrogen oxides, and further oxidative deterioration due to light,
We have found a new fact that the sensitivity and the repeating characteristics (durability) can be remarkably improved as compared with the conventional electrophotographic photoreceptor.

The effect of the combination of the charge generating material and the charge transporting material in the present invention is not necessarily clear, but the effect of suppressing oxidative deterioration caused by ozone, nitrogen oxides, etc. is considered as follows.
That is, in the diamine compound (2) used as the charge transport material, the delocalization of electrons is progressing, and the azo atom of the bisazo pigment (1) is sterically hindered by the phenyl group surrounding the nitrogen atom. It is considered that the coordination to the group is hindered and therefore the electron density of the azo group is not increased, so that it is less likely to be attacked by ozone and the like.

Furthermore, the bisazo pigment (1) has high charge generation efficiency and high sensitivity, and the diamine compound (2) has an ionic potential of bisazo pigment.
Since it has a good relationship with (1) and has excellent light resistance and durability, and has little dependence on the electric field strength of mobility, these characteristics are not reduced, and it becomes an optimum combination, which makes the electrophotographic photoreceptor It is considered that this has been achieved due to higher performance.

However, even with such a combination of the charge generating material and the charge transporting material, the printing speed is 40 to 5
When used in a high-speed copying machine of 0 sheets / minute, a large amount of ozone, nitrogen oxides, etc. are generated inside the machine, and the required amount of light is also large, so the photoconductor is exposed to a more severe use environment. Further improvement in durability against nitrogen oxides and the like is desired.

Therefore, in the present invention, in addition to the combination of the above specific charge generating material and charge transporting material, a general formula (3):

[0018]

[Chemical 9]

(Wherein Y ¹ and Y ² are the same or different and are alkylene groups, R ²⁰ , R ²¹ , R ²² and R ²³ are the same or different and are hydrogen atoms or alkyl groups, and R ²⁴ is a hydrogen atom and aralkyl groups. Or an aryl group, where r is 3 to 4
It is an integer of 0. ) Represented by the formula (4-a) or (4
-b):

[0020]

[Chemical 10]

(In the formula, one or both of R ²⁵ and R ²⁶ is a tert-butyl group, a tert-amyl group or an α, α-dimethylbenzylphenyl group, and one is a tert-butyl group or a tert-amyl group. Group or α,
When it is an α-dimethylbenzylphenyl group, the other is a hydrogen atom or an alkyl group. R ²⁷ represents a hydrogen atom, an alkyl group or a halogen atom. ) And a phenolic antioxidant.

That is, both of these stabilizers are intended to impart resistance to deterioration by oxidation against ozone, nitrogen oxides, and light. At that time, since the amine-based antioxidant (3) is an oligomer type and has a relatively high molecular weight, bleeding on the surface of the photosensitive layer is suppressed.
Since the phenolic antioxidants (4-a) and (4-b) have low molecular weight, they have a characteristic that they easily bleed on the surface.
Therefore, by combining both antioxidants, there are many phenolic antioxidants (4-a) and (4-b) on the surface of the photosensitive layer, and many amine antioxidants (3) are dispersed inside. As a result, even if the surface of the photosensitive layer is worn and scraped due to long-term use, the antioxidant effect is not impaired. Further, since the amine-based antioxidant (3) is an oligomer having an ester bond, it has an advantage that it has excellent adhesiveness for forming a photosensitive layer.

In the present invention, as the other stabilizer, an amine-based antioxidant which is the polyester oligomer represented by the general formula (3) and the general formula (5):

[0024]

[Chemical 11]

(Wherein R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ^37
38 are the same or different and include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group or an alkoxy group, and the alkyl group, the aralkyl group or the alkoxy group may have a substituent. It can also be used in combination with a benzotriazole-based ultraviolet absorber represented by the formula (1), and this also has the same effect as described above.

As the other stabilizer, the above-mentioned general formula is used.
An amine-based antioxidant that is a polyester oligomer represented by (3), and a general formula (6):

[0027]

[Chemical 12]

(Wherein R ⁴⁵ , R ⁴⁶ R ⁴⁷ R ⁴⁸ and R
⁴⁹ are the same or different and each is a hydrogen atom or an alkyl group. It can also be used in combination with an amine-based antioxidant represented by (4), and this also has the same effect as described above. Examples of the alkyl group in the general formula (1) include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group and a hexyl group. The group is raised. Examples of the aryl group include a phenyl group,
Examples thereof include o-terphenyl group, naphthyl group, anthryl group and phenanthryl group. Examples of the heterocyclic group include a thienyl group, a pyrrolyl group, a pyrrolidinyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a 2H-imidazolyl group,
Pyrazolyl group, triazolyl group, tetrazolyl group, pyranyl group, pyridyl group, piperidyl group, piperidino group, 3
-Morpholinyl group, morpholino group, thiazolyl group and the like. Further, the heterocyclic group may be condensed with an aromatic ring.

Substituents which may be substituted on the above groups include
For example, a halogen atom, an amino group, a hydroxyl group, a carboxyl group which may be esterified, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 2 to 2 carbon atoms. And the alkenyl group of 6 and the like. Examples of the coupler residue represented by A ¹ and A ² include groups represented by general formulas (a) to (g).

[0030]

[Chemical 13]

In each formula, R ³⁰ represents a carbamoyl group, a sulfamoyl group, an allofanoyl group, an oxamoyl group, an anthraniloyl group, a carbazoyl group, a glycyl group, a hydantoyl group, a phthalamoyl group, and a succinamoyl group. These groups, a halogen atom, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a nitro group, a cyano group, an alkyl group, an alkenyl group,
It may have a substituent such as a carbonyl group or a carboxyl group.

R ³¹ represents an atomic group necessary for forming an aromatic ring, a polycyclic hydrocarbon or a heterocyclic ring by being condensed with the above R ³⁰ and a benzene ring having a hydroxyl group, and these rings are as described above. You may have the same substituent. R ³² represents an oxygen atom, a sulfur atom or an imino group. R ³³ represents a divalent chain hydrocarbon or aromatic hydrocarbon, and these groups may have the same substituents as described above.

R ³⁴ represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group, and these groups may have the same substituents as described above. R ³⁵ is a divalent chain hydrocarbon, aromatic hydrocarbon, or the following formula (h) in the above general formulas (e) and (f):

[0034]

[Chemical 14]

It represents an atomic group necessary for forming a heterocycle with the moiety represented by, and these rings may have the same substituents as described above. R ³⁶ is a hydrogen atom, an alkyl group,
It represents an amino group, a carbamoyl group, a sulfamoyl group, an allofanoyl group, a carboxyl group, an ester of a carboxyl group, an aryl group, or a cyano group, and groups other than a hydrogen atom may have the same substituents as described above.

R ³⁷ represents an alkyl group or an aryl group, and these groups may have the same substituents as described above.
In R ³¹ , the atomic group necessary for forming an aromatic ring by condensing with R ³⁰ and a benzene ring having a hydroxyl group is, for example, a methylene group, an ethylene group, a propylene group,
Examples thereof include alkylene groups such as a butylene group.

The aromatic ring formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group is
Examples thereof include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, and naphthacene ring. In R ³¹ , the atomic group necessary for condensing with R ³⁰ and a benzene ring having a hydroxyl group to form a polycyclic hydrocarbon is, for example, a methylene group, an ethylene group, a propylene group, a butylene group, or a carbon atom. Examples include alkylene groups of the numbers 1 to 4.

In R ³¹ , the polycyclic hydrocarbon condensed with R ³⁰ and the benzene ring having a hydroxyl group includes, for example, a carbazole ring, a benzocarbazole ring and a dibenzofuran ring. Further, in R ³¹ , the atomic group necessary for condensing with R ³⁰ and a benzene ring having a hydroxyl group to form a heterocycle is, for example, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a 1H-indolyl group, a benzo Oxazolyl group, benzothiazolyl group, 1H-indadoryl group, benzimidazolyl group, chromenyl group, chromanyl group, isochromanyl group, quinolinyl group, isoquinolinyl group, cinnolinyl group, phthalazinyl group, quinazonilyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group , Xanthenyl group, acridinyl group, phenanthridinyl group, phenazinyl group, phenoxazinyl group, thianthrenyl group and the like.

Examples of the aromatic heterocyclic group formed by the condensation of R ³¹ with R ³⁰ and a benzene ring having a hydroxyl group include, for example, thienyl group, furyl group, pyrrolyl group, oxazolyl group, isoxazolyl group and thiazolyl group. , Isothiazolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group and thiazolyl group. It may also be a heterocyclic group condensed with another aromatic ring (for example, a benzofuranyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinolyl group).

In R ³³ and R ³⁵ , examples of the divalent chain hydrocarbon include ethylene group, propylene group and butylene group, and examples of the divalent aromatic hydrocarbon include phenylene group, naphthylene group, Examples thereof include a phenanthrylene group. Examples of the heterocyclic group for R ³⁴ include a pyridyl group, a pyrazyl group, a thienyl group, a pyranyl group and an indolyl group.

In R ³⁵ , the atomic group necessary for forming a heterocycle together with the moiety represented by the formula (h) is, for example, phenylene group, naphthylene group, phenanthrylene group, ethylene group, propylene group or butylene. Groups and the like. Examples of the aromatic heterocyclic group formed by R ³⁵ and the moiety represented by the formula (h) include, for example, benzimidazole group, benzo [f] benzimidazole group, dibenzo [e, g] benzimidazole group. Group, benzopyrimidine group and the like. These groups may have the same substituents as described above.

Examples of the carboxyl group ester in R ³⁶ include methyl ester, ethyl ester, propyl ester and butyl ester. Specific examples of the coupler residues A ¹ and A ² represented by the above general formulas (a) to (g) include the following groups.

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

Specific examples of the bisazo compound (1) include compounds represented by the following formulas (B1) to (B10).

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

In the diamine compound represented by the general formula (2), the alkyl group and aryl group corresponding to the groups R ^{2 to} R ⁷ in the formula include, for example, the groups represented by the general formula (1). The same thing is mentioned. Examples of the halogen atom include chlorine, iodine, bromine and fluorine. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a t-butoxy group and a hexyloxy group.

Examples of the alkylamino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group. , Hexylamino group and the like. Specific examples of the diamine-based compound represented by the general formula (2) include No. A shown in Table 1.
The compounds of 1 to A15 are mentioned. In the table, for example, “3-CH ₃ ” indicates that a methyl group is bonded to the 3-position of the phenyl group, and “3,5-CH ₃ ” is bonded to the 3-position and 5-position of the phenyl group. It shows that each methyl group is bonded.

[0053]

[Table 1]

The diamine compound (2) can be synthesized by various methods. For example, the following general formula (40)
It can be produced by reacting the compound represented by and the compounds represented by the general formulas (41) to (44) simultaneously or sequentially.

[0055]

[Chemical formula 22]

(Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , k, l, m, o, p, and q are the same as above. X
Represents a halogen atom. ) The reaction of the compound represented by the general formula (40) with the compound represented by the general formulas (41) to (44) is
Usually performed in an organic solvent, any solvent can be used as long as it does not adversely affect this reaction,
For example, organic solvents such as nitrobenzene, dichlorobenzene, quinoline, N, N-dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide are exemplified. The reaction is usually carried out in the presence of a catalyst such as copper powder, copper oxide, copper halide, etc., and a basic substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. It is carried out at a temperature of 250 ° C.

Further, the compound represented by the general formula (2) having a symmetric structure is controlled in the substitution position of the substituents R ² , R ³ , R ⁴ and R ⁵ , for example, the following general formula (45) ) And a compound represented by the general formula (41), (43) to obtain a compound represented by the following general formula (46), then the compound represented by the general formula (46) Can be produced by hydrolyzing and deacylating to obtain a compound represented by the following general formula (47), and further reacting it with a compound represented by the general formulas (42) and (44). .

[0058]

[Chemical formula 23]

(In the formula, R ⁸ and R ⁹ represent an alkyl group, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , k, l,
m, o, p, and q are the same as above. ) The above general formula (45)
The reaction of the compound represented by the general formula (41) with the compound represented by the formula (43), the compound represented by the general formula (40) and the general formula (4
It can be carried out in the same manner as the reaction with the compounds represented by 1) (42) (43) (44). The deacylation reaction of the compound represented by the general formula (46) by hydrolysis can be carried out by a conventional method in the presence of a basic catalyst. Further, the reaction of the compound represented by the general formula (47) and the compound represented by the general formula (42) (44), the compound represented by the general formula (40) and the general formula (41) ( Four
2) It can be carried out in the same manner as the reaction with the compounds represented by (43) and (44).

After completion of the reaction, the reaction mixture can be concentrated and easily separated and purified by a conventional means such as recrystallization, solvent extraction, column chromatography and the like. Next, the stabilizer added to the photosensitive layer will be described. (I) When used in combination with the oligomeric amine antioxidant of the general formula (3) and the phenolic antioxidant of the general formula (4).

Specific examples of the alkyl group, alkoxyl group and aryl group in the general formulas (3) and (4) are:
Examples thereof include the same groups as those groups in the general formula (1) or (2). Moreover, examples of the aralkyl group include a benzyl group, a benzhydryl group, a trityl group, and a phenethyl group. Specific compounds of the oligomeric amine-based antioxidant (3) include, for example, compounds (F1) to (F6) represented by the following formulas.

[0062]

[Chemical formula 24]

The addition amount of the oligomeric amine antioxidant (3) is usually 0.5 to 20 parts by weight with respect to 100 parts by weight of the binder resin. Specific compounds of the phenolic antioxidant (4-a) and (4-b) are:
For example, the compounds of (G1) to (G6) represented by the following formulas can be mentioned.

[0064]

[Chemical 25]

The amount of the phenolic antioxidants (4-a) and (4-b) added is usually about 1 to 30 parts by weight based on 100 parts by weight of the binder resin. (II) When used in combination with the oligomeric amine antioxidant of the general formula (3) and the benzotriazole ultraviolet absorber of the general formula (5). Examples of the benzotriazole-based ultraviolet absorber of the general formula (5) include the following.

[0066]

[Chemical formula 26]

The addition amount of the oligomeric amine antioxidant (3) in combination with such a benzotriazole ultraviolet absorber may be the same as above. Further, the addition amount of the benzotriazole-based ultraviolet absorber (5) is usually about 1 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Also, oligomeric amine antioxidants
In the combination of (3) and the benzotriazole-based ultraviolet absorber (5), the stabilizer shown below may be added in order to further enhance the stabilizing effect. (1) The phenolic antioxidant represented by the above general formula (4-a) or (4-b), (2) the general formula (7):

[0068]

[Chemical 27]

(In the formula, R ⁴¹ and R ⁴² are the same or different and each is a hydrogen atom, an alkyl group, a cyclohexyl group or a dimethylbenzylphenyl group, and Y ³ is an alkylene group.), (3) General formula
(8):

[0070]

[Chemical 28]

(In the formula, R ⁴¹ and R ⁴² are the same as described above, Y
⁴ is an alkylene group, Y ⁵ is an alkylene group or an alkylene glycol residue. ) A phenolic antioxidant represented by (4) the general formula (9)

[0072]

[Chemical 29]

(Wherein R ⁴¹ and R ⁴² are the same as those described above, E
Is based on:

[0074]

[Chemical 30]

(In the formula, R ⁵⁶ is a hydrogen atom or an alkyl group.) And Y ⁶ is an alkylene group, an alkylenecarbonyloxyalkyl group or an alkyleneoxycarbonylalkyl group. ) Or a phenolic antioxidant represented by the general formula (10):

[0076]

[Chemical 31]

(In the formula, R ⁵⁰ and R ⁵¹ are the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group or a dimethylbenzylphenyl group, R ⁵² , R ⁵³ , R ⁵⁴ and R ^54.
55 is the same or different and is a hydrogen atom or an alkyl group. ) A piperidine-based antioxidant represented by: Examples of the alkylene group include methylene group, ethylene group, propylene group, tetramethylene group, pentamethylene group and hexamethylene group.

As the alkylene glycol residue,
For example -Y ⁵ -Y ⁵ - as, triethylene glycol residue, tripropylene glycol residues, tetraethylene glycol residues, pentaethylene glycol residues, and the like. Examples of the alkylenecarbonyloxyalkyl group include a methylenecarbonyloxymethyl group,
Examples thereof include an ethylenecarbonyloxypropyl group, a butylenecarbonyloxymethyl group, a hexamethylenecarbonyloxymethyl group, a methylenecarbonyloxypropyl group and a pentamethylenecarbonyloxyhexyl group.

Examples of the alkyleneoxycarbonylalkyl group include methyleneoxycarbonylmethyl group, ethyleneoxycarbonylpropyl group, butyleneoxycarbonylmethyl group, hexamethyleneoxycarbonylmethyl group, methyleneoxycarbonylpropyl group, pentamethyleneoxycarbonyl group. Hexyl group and the like can be mentioned.

Specific compounds of these additives (7) to (10) are shown in Tables 2 to 5, respectively.

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

All of these compounds (7) to (10) have the purpose of imparting resistance to oxidation deterioration by ozone, nitrogen oxides and light, and at the same time, the above-mentioned oligomeric amine antioxidant (3) And benzotriazole UV absorber
By combining with (5), the light resistance and nitrogen oxide resistance are further improved and a high stabilizing effect is exhibited. Also,
The phenol-based antioxidant of the general formula (8) and the piperidine-based antioxidant of the general formula (10) may be used alone or in combination. As for other antioxidants, if necessary, two kinds or three kinds or more may be mixed and used. (III) When used in combination with the oligomeric amine-based antioxidant of the general formula (3) and the amine-based antioxidant of the general formula (6).

Examples of the amine antioxidant represented by the above general formula (6) include those shown in Table 6.

[0087]

[Table 6]

The function of the amine antioxidant (6) is almost the same as that of each of the above antioxidants. The addition amount of the oligomeric amine-based antioxidant (3) in combination with the amine-based antioxidant (6) may be the same as above. Further, the addition amount of the amine-based antioxidant (6) is usually about 0.5 to 20 parts by weight with respect to 100 parts by weight of the binder resin.

The photoconductor of the present invention can be applied to either a single layer type or a laminated type as a photosensitive layer. However, since the effect of the combination of the charge generating material and the charge transporting material becomes more remarkable especially in the single layer type photosensitive layer in which both materials are contained in the same layer, the present invention provides a single layer type photosensitive layer. It can be said that it is more preferable to apply it to the provided electrophotographic photoreceptor.

To obtain a single-layer type photoreceptor, a photosensitive material containing the bisazo pigment (1) which is a charge generating material, the diamine compound (2) which is a charge transporting material, a binder resin and the like. The layer may be formed on the conductive substrate by means such as coating. Further, in order to obtain a laminated type photoreceptor, the above bisazo pigment is formed on a conductive substrate by means such as vapor deposition or coating.
A charge generation layer containing (1) and a binder resin may be formed, and a charge transport layer containing the diamine compound (2) and the binder resin may be formed on the charge generation layer. Alternatively, conversely to the above, the charge transport layer may be formed on the conductive substrate, and then the charge generation layer may be formed.

As the charge generating material, in addition to the bisazo pigment (1), for the purpose of expanding the sensitivity region of the electrophotographic photosensitive member so as to have an absorption wavelength region in a desired region,
Further, other conventionally known charge generating materials can be used together. Other charge generating materials include other azo pigments having a different chemical structure from that represented by the general formula (1),
Selenium, selenium-tellurium, selenium-arsenic, amorphous silicon, pyrylium salt, perylene pigments, ansanthuron pigments, phthalocyanine pigments, naphthalocyanine pigments, indigo pigments, triphenylmethane pigments, threnic pigments, toluidine pigments. Pigments, pyrazoline pigments, quinacridone pigments, dithioketopyrrolopyrrole pigments and the like can be mentioned.

The diamine-based compound as a charge transport material
(2) can be used alone or in combination with other conventionally known charge transport materials. As the conventionally known charge transport material, various electron-withdrawing compounds and electron-donating compounds can be used. As the electron-withdrawing compounds, such as ^{2,6-dimethyl-2,, 6,} - di te
Diphenoquinone derivatives such as rt-dibutyldiphenoquinone, malononitrile, thiopyran compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone,
Examples include fluorenone compounds (3,4,5,7-tetranitro-9-fluorenone, etc.), dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromomaleic anhydride, etc. To be done.

As the electron donating compound, 2,5
-Oxadiazole compounds such as di (4-methylaminophenyl) and 1,3,4-oxadiazole, 9- (4
-Styryl compounds such as diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, triphenylamine compounds, indole Compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds,
Examples thereof include nitrogen-containing cyclic compounds such as imidazole compounds, pyrazole compounds, and triazole compounds, and condensed polycyclic compounds.

These charge transport materials may be used alone or in combination of two or more. When a charge transporting material having film-forming property such as polyvinylcarbazole is used,
The binder resin is not always necessary. Various resins can be used as the binder resin. For example, styrene-based polymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene, ethylene-vinyl acetate copolymer , Chlorinated polyethylene, polyvinyl chloride, polypropylene,
Thermoplastic resins such as vinyl chloride-vinyl acetate copolymer, polyester alkyd resin, polyamide, polyurethane, polycarbonate, polyarylate, polysulfone, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin, and the like,
Examples thereof include silicone resins, epoxy resins, phenol resins, urea resins, melamine resins, other crosslinkable thermosetting resins, and photocurable resins such as epoxy acrylate and urethane-acrylate. These binder resins are 1
One kind or a mixture of two or more kinds can be used.

The single-layer type organic photosensitive layer and the laminated type organic photosensitive layer include
A sensitizer, a fluorenone-based compound, an antioxidant, a deterioration inhibitor such as an ultraviolet absorber, and an additive such as a plasticizer can be contained. Further, in order to improve the sensitivity of the charge generation layer, known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generation material.

In the laminated photoreceptor, the charge generating material and the binder resin constituting the charge generating layer can be used in various ratios, but the charge generating material 5 to 5 parts by weight relative to 100 parts by weight of the binder resin. It is preferably used in an amount of 1000 parts by weight, particularly 30 to 500 parts by weight. The charge transport material constituting the charge transport layer and the binder resin can be used in various proportions within a range that does not hinder the transport of charges and a range that does not crystallize, but they are generated in the charge generation layer by light irradiation. 10 to 500 parts by weight of the charge transport material, particularly 25 to 100 parts by weight of the binder resin so that the charges can be easily transported.
It is preferably used in a proportion of 200 parts by weight.

The thickness of the laminated photosensitive layer is preferably 0.01 to 5 μm, particularly 0.1 to 3 μm for the charge generation layer, and 2 to 100 μm for the charge transport layer.
m, particularly preferably about 5 to 50 μm.
In a single-layer type photoreceptor, the charge generation material is 0.1 to 50 parts by weight, particularly 0.5 to 100 parts by weight with respect to the binder resin.
30 parts by weight, 20 to 500 parts by weight of the charge transport material, particularly 30 to 200 parts by weight are suitable. The thickness of the single-layer type photosensitive layer is 5 to 100 μm, particularly 10 to 50 μm.
It is preferable that the thickness is about m.

In the case of a single-layer type photoreceptor, it is between a conductive substrate and a photosensitive layer, and in the case of a laminated type photoreceptor, it is between a conductive substrate and a charge generating layer, and a conductive substrate. A barrier layer may be formed between the charge transport layer and the charge transport layer or between the charge generation layer and the charge transport layer to the extent that the characteristics of the photoreceptor are not impaired. It may be formed.

As the conductive substrate on which the above layers are formed, various conductive materials can be used.
For example, simple metals such as aluminum, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass, a plastic material in which the above metal is vapor-deposited or laminated, iodide Examples thereof include glass coated with aluminum, tin oxide, indium oxide, or the like.

The conductive substrate may be in the form of a sheet, a drum or the like, as long as the substrate itself has conductivity or the surface of the substrate has conductivity. Further, it is preferable that the conductive substrate has sufficient mechanical strength when used. When each of the above layers is formed by a coating method, the charge generating material, charge transporting material, binder resin and the like exemplified above are combined with a suitable solvent by a known method, for example, a roll mill, a ball mill, an attritor, a paint shaker. Alternatively, an ultrasonic disperser or the like may be used for dispersion and mixing to prepare a coating solution, which may be coated and dried by a known means.

As the solvent for forming the coating solution, various organic solvents can be used, for example, alcohols such as methanol, ethanol, isopropanol and butanol,
Aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, dimethyl ether, diethyl ether and tetrahydrofuran. , Ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, dimethylformaldehyde, dimethylformamide and dimethyl sulfoxide. These solvents can be used alone or in combination of two or more.

Furthermore, in order to improve the dispersibility of the charge transport material or the charge generating material and the smoothness of the surface of the photosensitive layer, a surfactant, a leveling agent, etc. may be used.

[0103]

The present invention will be described in detail below with reference to examples and comparative examples. Examples 1 to 6 (multilayer photoreceptor) 0.7 parts by weight of a bisazo pigment which is a charge generating material, 1 part by weight of polyvinyl butyral resin and a predetermined amount of tetrahydrofuran are used as paint shakers using glass beads (2 mm diameter). And dispersed for 2 hours. The obtained dispersion liquid was applied onto the surface of an aluminum tube by a dip coating method and dried at 100 ° C. for 1 hour to form a charge generation layer having a film thickness of 0.5 μm.

On this charge generation layer, 1 part by weight of a diamine compound as a charge transporting material and 1 part by weight of a bisphenol A type polycarbonate resin were dissolved in a predetermined amount of dichloromethane, and further, as a stabilizer, an oligomeric amine type antioxidant was used. A solution in which the agent and the phenolic antioxidant were added at the ratio shown in Table 7 was applied by a dip coating method, and 10
A charge transport layer having a film thickness of 22 μm was formed by drying at 0 ° C. for 1 hour to obtain a negative charging type laminated electrophotographic photoreceptor. The charge generation material and charge transport material used in each example are
It shows in Table 7 using the compound number of each specific example mentioned above. Comparative Example 1 (Layered Photoreceptor) A negative charge type was prepared in the same manner as in Examples 1 to 6 except that the bisazo pigment and the diamine compound represented by the compound numbers in Table 7 were used without adding the stabilizer. A laminated electrophotographic photoreceptor was obtained. Comparative Examples 2 to 7 (Layered Photoreceptor) Compounds represented by the following formulas (D1) to (D5) and (D11) were used in place of the diamine compounds used in Examples 1 to 6, and stable. Negatively charged layered electrophotographic photoreceptors were obtained in the same manner as in Examples 1 to 6 except that no agent was added.

[0105]

[Chemical 32]

[0106]

[Chemical 33]

[0107]

[Table 7]

Examples 7 to 12 (single-layer type photoreceptor) 3 parts by weight of a bisazo pigment which is a charge generating material, 75 parts by weight of a diamine compound which is a charge transporting material, and 100 parts by weight of a bisphenol A type polycarbonate resin. For the single-layer type photosensitive layer, the oligomer type amine-based antioxidant and the phenol-based antioxidant as stabilizers in the compounding ratios shown in Table 8 were dispersed together with dichloromethane for 2 minutes using an ultrasonic disperser. A coating solution of was prepared. Then, this coating solution is applied to the surface of the aluminum tube by a dip coating method and dried at 80 ° C. for 120 minutes to form a single-layer type photosensitive layer having a film thickness of 30 μm. An electrophotographic photoreceptor was obtained. The respective charge generating materials and charge transporting material compounds used are shown in Table 8 by using the compound numbers of the above specific examples.
It was shown to. Comparative Example 8 (Single-Layer Photoreceptor) A positively charged type was prepared in the same manner as in Examples 7 to 12 except that the bisazo pigment and the diamine compound represented by the compound numbers in Table 8 were used without adding the stabilizer. A single-layer type electrophotographic photoconductor of was obtained. Comparative Examples 9 to 14 (single-layer type photoconductor) Instead of the diamine compounds used in Examples 7 to 12,
Using the compounds represented by the following formulas (D6) to (D11),
And Examples 7-12 except that no stabilizer was added.
In the same manner as described above, a positive charging type single-layer type electrophotographic photosensitive member was obtained.

[0109]

[Chemical 34]

[0110]

[Chemical 35]

[0111]

[Table 8]

The following tests were carried out on the electrophotographic photosensitive members of the above Examples and Comparative Examples to evaluate their characteristics. Electrical Properties After measuring the surface potential (V) when the surface of the electrophotographic photosensitive member prepared in each Example and Comparative Example was charged to around ± 800 V, the light of 550 nm most necessary for the photosensitive member for PPC was measured. The half-exposure amount was measured by using. That is, the wavelength extracted from the xenon lamp using the spectrometer is 550.
nm light was exposed at an intensity of 0.2 mW / cm ² and an exposure time of 1 second to determine the half-dose exposure amount (μJ / cm ² ). Also,
The surface potential at the time point 0.5 seconds after the light irradiation was determined as the post-exposure potential (V). Repeating characteristics 1 with electrostatic copying machine DC-1670M (manufactured by Mita Industry Co., Ltd.)
Surface potential (V) after repeated printing of 10,000 times,
The half-dose exposure amount (μJ / cm ² ) and the post-exposure potential (V) were measured.

The test results described above are shown in Tables 9 and 10.

[0114]

[Table 9]

[0115]

[Table 10]

As is clear from Tables 9 and 10, Comparative Example 2
Each of the photoconductors obtained in Nos. 7 to 9 and 14 has poor sensitivity, and therefore has fog from the beginning of printing, and corresponds to a white background even if the exposure lamp, which is standardly installed in the electrostatic copying machine, outputs the maximum light. The potential was high and fogging occurred. Further, in the image confirmation after repeated printing, the contrast potential was decreased due to the decrease in the surface potential, and the image density was also decreased.
On the other hand, in the photoconductors obtained in Comparative Examples 1 and 8, the initial sensitivity was almost the same as that of the example, but the sensitivity was remarkably lowered after the repeated printing.

On the other hand, all the photoconductors of the respective examples had high sensitivity, and a clear image was obtained even at a normal exposure intensity, and a good image was obtained by repeated printing. Examples 13 to 18 (laminated photoreceptor) and Examples 19 to
24 (single layer type photoreceptor) as a charge generating material, charge transporting and stabilizing agent
1, Examples 1 to 6 except that the components shown in Table 12 were used
And, in the same manner as in Examples 7 to 12, laminated-type and single-layer-type photoreceptors were prepared.

[0118]

[Table 11]

[0119]

[Table 12]

Examples 25 to 30 (multilayer type photoreceptor) and
Examples 31 to 36 (single-layer type photoreceptor) As a charge generating material, charge transporting and stabilizing agent, Table 1
3, Examples 1 to 6 except that the components shown in Table 14 were used
And, in the same manner as in Examples 7 to 12, laminated-type and single-layer-type photoreceptors were prepared.

[0121]

[Table 13]

[0122]

[Table 14]

Examples 13 to 30 and Examples 19 to 36
Table 15 shows the electric characteristics obtained in the same manner as above, and Table 16 shows the test results of the repeated characteristics obtained in the same manner as above.

[0124]

[Table 15]

[0125]

[Table 16]

From these test results, it can be seen that each of the photoconductors has a high sensitivity, a clear image can be obtained even at a normal exposure intensity, and a good image can be obtained by repeated printing.

[0127]

According to the present invention, a bisazo pigment represented by the general formula (1), which is a charge generating material, and a diamine compound represented by the general formula (2), which is a charge transport material, are used. Further, by using a specific antioxidant or the like as a stabilizer, it is possible to obtain an organic photoreceptor having high sensitivity and excellent repeating characteristics.

Claims (3)

[Claims] 1. A general formula (1) as a charge generating material: (In the formula, A ¹ and A ² are the same or different and each represents a coupler residue, R ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the alkyl group, the aryl group and the heterocyclic group represent Which may have a substituent, n represents 0 or 1, and a bisazo pigment represented by the general formula (2): (In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and represent an alkyl group, an alkoxyl group, a halogen atom, an aryl group, a nitro group, a cyano group or an alkylamino group. p and q represent an integer of 0 to 3. k,
l, m and o each represent an integer of 0-2. ) And a diamine compound represented by the general formula (3): (In the formula, Y ¹ and Y ² are the same or different and are alkylene groups, R ²⁰ , R ²¹ , R ²² and R ²³ are the same or different and are hydrogen atoms or alkyl groups, and R ²⁴ is a hydrogen atom, aralkyl group or aryl group. Wherein r is an integer of 3 to 40) and an amine-based antioxidant which is a polyester oligomer and is represented by the general formula (4-a) or (4-b): (In the formula, one or both of R ²⁵ and R ²⁶ are t
ert-butyl group, tert-amyl group or α, α-
A dimethylbenzylphenyl group, one of which is tert-
When it is a butyl group, a tert-amyl group or an α, α-dimethylbenzylphenyl group, the other is a hydrogen atom or an alkyl group. R ²⁷ represents a hydrogen atom, an alkyl group or a halogen atom. ) An electrophotographic photoreceptor comprising a conductive layer and a photosensitive layer containing a phenolic antioxidant represented by the formula (4). 2. The general formula of the charge generating material according to claim 1.
A bisazo pigment represented by the formula (1) and a diamine compound represented by the general formula (2), which is the charge-transporting material according to claim 1, and a general formula according to claim 1 as a stabilizer.
An amine-based antioxidant, which is a polyester oligomer represented by (3), and a general formula (5): (In the formula, R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group or an alkoxy group, and an alkyl group, an aralkyl group or an alkoxy group. The group may have a substituent.) An electrophotographic photoreceptor comprising a photosensitive layer containing a benzotriazole-based ultraviolet absorber represented by the formula) on a conductive substrate. 3. The general formula of the charge generating material according to claim 1.
A bisazo pigment represented by the formula (1) and a diamine compound represented by the general formula (2), which is the charge-transporting material according to claim 1, and a general formula according to claim 1 as a stabilizer.
An amine-based antioxidant, which is a polyester oligomer represented by (3), and a general formula (6): (Wherein R ⁴⁵ , R ⁴⁶ R ⁴⁷ R ⁴⁸ and R ⁴⁹ are the same or different and each is a hydrogen atom or an alkyl group) and a photosensitive layer containing an amine antioxidant represented by the formula An electrophotographic photosensitive member characterized in that it is provided in the.