JPH0649433A - Photoconductive composition and electrophotographic photoreceptor using the same - Google Patents

Abstract

PURPOSE:To obtain a photoconductive composition consisting of a specific trisazo pigment and a specific disazo pigment, having high sensitivity in broad wavelength area and capable of providing an electrophotographic photoreceptor reduced in deterioration of charging properties due to ozone and NOx gas. CONSTITUTION:The composition consists of (A) a trisazo pigment of formula I (R<1> is H, halogen, alkyl, etc.; D is coupler residue) and (B) a disazo pigment of formula II, formula III (R<2> and R<3> are R<1>; A and B are coupler residues), etc. The component A and the component B are preferably blended in the range of a weight ratio expressed by the formula 0.1<= component (B)/ components (A)+(B)<=0.9. Furthermore, as the component A, a compound of formula IV, etc., is preferable, because the compound has broad sensitive wavelength area and a photoreceptor highly sensitive to LD light having 780-850nm wavelength is obtained by mixing the compound with the component B. As the component B, a compound of formula V, etc., is preferably used, because the compound has high sensitivity in visible light area and when mixed with the component A, the resultant composition has good stabiity in coating liquid in which pigment is dispersed and can form good coating film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductive composition useful for electrophotographic photoconductors, solar cells, photosensors, optical switching elements and the like, and electrophotographic photoconductors using the same.

[0002]

2. Description of the Related Art In recent years, the development of information processing system machines using electrophotography has been remarkable. In particular, an optical printer that converts information into a digital signal and records information by light has excellent print quality and reliability. This digital recording technology is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. Further, since various conventional information processing functions are added to a copying machine equipped with this digital recording technology in the conventional analog copying, it is expected that the demand will be further increased in the future.

As a light source for an optical printer, a semiconductor laser (LD) and a light emitting diode (LED) which are small in size, inexpensive and highly reliable are currently widely used. However,
The light emission wavelength of the LED that is currently widely used is 660 nm, while the light emission wavelength range of the LD is in the near infrared region. Therefore, development of an electrophotographic photoreceptor having high sensitivity in the visible light region to the near infrared light region is desired.

However, the photosensitive wavelength range of the electrophotographic photosensitive member is substantially determined by the photosensitive wavelength range of the charge generating substance (CGM) used in the photosensitive member. Therefore, many CGMs have been conventionally developed, but a single CGM having sufficiently high sensitivity in a wide photosensitive wavelength range from the visible light region to the near infrared light region has not yet been developed.

Therefore, conventionally, a CGM (short-wavelength CGM) having a high sensitivity to visible light and a CGM (long-wavelength CGM) having a sensitivity to near-infrared light are mixed to obtain a photosensitive member having a wide photosensitive wavelength range. Various designs have been attempted.
For example, (a) a trisazo pigment, (b) one or more kinds of perinone pigments and anzanthuron pigments, and (c) an electron-donating substance are contained, so that electrophotography having sensitivity to white light, gas laser, and LED. A printing plate for plate-making (JP-A-3-146957) and an electrophotographic photoreceptor having sensitivity to white light and infrared laser by using a disazo pigment and oxotitanium phthalocyanine together (JP-A-3-196049). ), Or a mixture of trigonal selenium particles and phthalocyanine particles using a styrene-butadiene copolymer as a binder in a charge generation layer containing a mixed pigment, and having photosensitivity in the visible to infrared light region. Photoconductors (JP-A-3-225346) have been proposed. In addition, it has been announced that the photosensitivity of phthalocyanine is sensitized by mixing a perylene pigment and a β-type phthalocyanine pigment [Kawahara et al .: "Perylene pigment / phthalocyanine pigment intermolecular interaction and electrophotographic characteristics of an organic photoreceptor. »Proceedings of the 62nd Autumn Meeting of the Chemical Society of Japan
II P868 (1991); Kawahara et al., "Effect of Phthalocyanine Addition to Organic Single-Layer Photoreceptor Using Perylene Pigment", 68th
Proceedings of the Annual Meeting of the Electrophotographic Society of Japan P72-P75 (1
991)].

[0006]

However, these photoreceptors are deteriorated in their charging characteristics due to exposure to ozone and NOx gas generated from the charge of a copying machine or printer, and sufficient characteristics are obtained. Absent.

Therefore, an object of the present invention is to have a higher sensitivity in a wider wavelength range than a case where a photosensitive member is designed by using each CGM alone by mixing a short wavelength CGM and a long wavelength CGM, and It is an object of the present invention to provide a photoconductive composition capable of obtaining a photoconductor for electrophotography which is less likely to be deteriorated in charging characteristics due to ozone or NOx gas, and a photoconductor for electrophotography using the same.

[0008]

According to the present invention, it comprises one or more trisazo pigments represented by the following general formula 1 and one or more disazo pigments represented by the following general formulas 2 to 8. A photoconductive composition is provided.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8] (However, in the above general formulas 1 to 8, A, B and D
Represents a coupler residue and may be the same or different, and R ^{1 to} R ⁷ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group and may be the same or different. )

Further, according to the present invention, in a photoconductor for electrophotography comprising a photoconductive layer formed on a conductive support, one or more kinds of the following general formula 1 are contained in the photoconductive layer. An electrophotographic photoreceptor is provided, which contains a trisazo pigment described above and one or more disazo pigments represented by the following general formulas 2 to 8.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8] (However, in the above general formulas 1 to 8, A, B and D
Represents a coupler residue and may be the same or different, and R ^{1 to} R ⁷ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group and may be the same or different. )

Since the photoconductive composition of the present invention is composed of a specific disazo pigment having a high sensitivity to visible light and a specific trisazo pigment having a sensitivity to light of 700 nm or longer, It has a high sensitivity in a wide wavelength range, does not reduce the sensitivity to visible light, and has less deterioration of charging characteristics due to ozone or NOx gas.

The mixing ratio of the disazo pigment and the trisazo pigment in the photoconductive composition of the present invention depends on the types of pigments to be mixed, for example, in consideration of the required characteristics (sensitivity, charging characteristics, gas resistance) of the photoreceptor. The optimum value can be selected individually, but it is generally preferable that the weight ratio is in the range of 0.01 ≦ disazo pigment / (disazo pigment + trisazo pigment) ≦ 0.99. When it is lower than 0.01, the sensitivity sensitizing effect is small, and when it is higher than 0.99, the sensitizing effect and the gas resistance are less improved. Further, considering the uniformity of the spectral sensitivity from the visible light wavelength region to the near infrared light wavelength region, the range of 0.1 ≦ disazo pigment / (disazo pigment + trisazo pigment) ≦ 0.9 is desirable.

As the electrophotographic photoreceptor, a charge generating layer containing a charge generating substance which absorbs light to generate a charge carrier on a conductive support, and the charge carrier is easily injected and transports it. A photoconductive layer composed of a charge transporting layer containing a charge transporting substance having a capability, a so-called laminated photoconductor (or a function separation type photoconductor), and a charge generating substance and a charge transporting substance on a conductive support. There is a single-layer photoconductor (or dispersion photoconductor) provided with a photoconductive layer consisting of a single layer dispersed in a binder resin. The photoconductive composition of the present invention can be applied to any of the above photoconductors.

The composition comprising the disazo pigment and the trisazo pigment of the present invention mainly functions as a charge generating substance. The charge generating substance in the photoconductive layer needs to be as small as possible in order to efficiently absorb light and effectively inject the generated charge carriers into the charge transporting substance. 1 μm or less is preferable. However, in the azo pigment after synthesis, fine particles of 0.1 μm or less are aggregated to form 0.1 to 1
The secondary particles are 0 mm, and if the charge generation layer is formed in this state, insufficient sensitivity can be obtained. Therefore,
Usually, the secondary particles are crushed into smaller aggregated particles or primary particles having a particle size of 0.1 μm or less, and then used for forming the charge generation layer. Also in the present invention, the disazo pigment and the trisazo pigment are pulverized and used.

The charge generation layer of the laminated photoreceptor and the photoconductive layer of the single-layer photoreceptor containing the composition comprising the disazo pigment and the trisazo pigment of the present invention are formed on the conductive support by the following method. . At least one type of trisazo pigment and at least one type of disazo pigment are separately added to a suitable dispersion medium, if necessary, a binder resin and a charge transport substance, and then a ball mill, a vibration mill, a disk vibration mill, an attritor. The pigment is pulverized and dispersed into particles having a particle size of 1 μm or less by using a sand mill, an ultrasonic dispersion device, or the like, and then a mixed dispersion liquid prepared by mixing these liquids is applied onto the conductive support. At least one of the trisazo pigments and at least one of the disazo pigments are added together in a suitable dispersion medium, and if necessary, a binder resin and a charge transporting substance are added to the dispersion device as shown in The dispersion liquid obtained by pulverizing and mixing fine particles is applied onto a conductive support. In the case of a laminated photoreceptor, a charge transport layer is laminated on the charge generation layer formed in to form the photoreceptor.

Whichever of the above methods is used, in the combination of the disazo pigment and the trisazo pigment of the present invention, the sensitivity in the long wavelength region of 700 nm or more is longer than that in the case where the photoreceptor is prepared by using the trisazo pigment alone. The deterioration of charging characteristics due to gases such as NO and ozone is remarkably improved without decreasing the value, but when the method is used in particular (that is, when a simultaneous pulverized mixture obtained by pulverizing both pigments and then pulverizing is used). Is significantly sensitized by 1.5 to 2.5 times the sensitivity in the long wavelength region as compared with the case of using the trisazo pigment alone. Currently, the reason for this sensitizing effect is not clear.

As described above, the photoconductive composition of the present invention comprises one or more trisazo pigments represented by the following general formula 1 and one or more disazo pigments represented by the following general formulas 2-8. It consists of and.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8] (However, in the above general formulas 1 to 8, A, B and D
Represents a coupler residue and may be the same or different, and R ^{1 to} R ⁷ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group and may be the same or different. )

In particular, in the tris- and bisazo pigments, the coupling residues represented by A, B and D in the general formulas 1 to 8 are represented by the following general formula 9
Those selected from the residues represented by Chemical formula 14 are preferable.

[Chemical 9] [However, in the above formula, X ¹ , Y ¹ and Z respectively represent the following. ^{X 1: -OH, -N (R} 8) (R 9) or, -NHSO ₂ -
R ¹⁰ . (R ⁸ and R ⁹ represent a hydrogen atom, an acyl group or a substituted or unsubstituted alkyl group, and R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Y ¹ : hydrogen atom A halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxy group, a sulfone group, a benzimidazolyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted allofanoyl group or -CON (R ¹¹ ) (Y ² ) Is represented. {R ¹¹ represents a hydrogen atom, an alkyl group or a substituted product thereof, or a phenyl group or a substituted product thereof, and Y ² is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or -N = C (R ¹² ) (R ¹³ ) (wherein R ¹² is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, a styryl group or a substituted product thereof, and R ¹³ is a hydrogen atom, an alkyl group or a substituted product thereof, or phenyl Represents a group or a substituent thereof, or R ¹² and R ¹³ may form a ring together with the carbon atom bonded to them. } Z: Hydrocarbon ring group or a substituted body thereof, or heterocyclic group or a substituted body thereof. ]

[Chemical 10] (In the above formula, R ¹⁴ represents a substituted or unsubstituted hydrocarbon group.)

[Chemical 11] (In the above formula, R ¹⁵ represents a substituted or unsubstituted hydrocarbon group.)

[Chemical 12] (In the above formula, R ¹⁶ represents an alkyl group, a carbamoyl group, a carboxyl group or an ester thereof, and Ar represents a substituted or unsubstituted aromatic hydrocarbon group.)

[Chemical 13] (In the above formula, X ² represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group.)

[Chemical 14] (In the above formula, X ² represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group.)

Specific examples of the coupler of the azo pigment used in the present invention, that is, specific examples of AH, BH and DH are shown in Tables 1 to 21.

[0019]

[Table 1- (1)]

[0020]

[Table 1- (2)]

[0021]

[Table 1- (3)]

[0022]

[Table 2- (1)]

[0023]

[Table 2- (2)]

[0024]

[Table 3- (1)]

[0025]

[Table 3- (2)]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

[Table 7]

[0030]

[Table 8]

[0031]

[Table 9]

[0032]

[Table 10]

[0033]

[Table 11]

[0034]

[Table 12- (1)]

[0035]

[Table 12- (2)]

[0036]

[Table 12- (3)]

[0037]

[Table 13- (1)]

[0038]

[Table 13- (2)]

[0039]

[Table 13- (3)]

[0040]

[Table 14- (1)]

[0041]

[Table 14- (2)]

[0042]

[Table 15]

[0043]

[Table 16]

Of the azo pigments described above, the trisazo pigments are particularly preferably compounds represented by the following general formulas 15, 16, and 17. This is because the trisazo compound represented by the general formula 15 is a material having a high charge generation ability by irradiation with light in the near infrared region (700 nm or longer), and when mixed with a disazo pigment, it is visible to the near infrared region. It is possible to produce a photoconductor having high photosensitivity over a wide range,
The trisazo compound represented by has a wide photosensitive wavelength range up to around 850 nm, and by mixing with a disazo pigment, a photoconductor having high sensitivity to LD light (780 to 850 nm) can be prepared. Is possible.

[0045]

[Chemical 15] (However, in the formula, R ^{21 to} R ²⁹ are a hydrogen atom, —CH ₃ , or —C ₂
H _5, -C ₃ H _7, a chlorine atom, a fluorine atom, an iodine atom, a bromine _{atom, CH 3 O-, C 2 H} 5 O-, C 3 H 7 O -, - NO 2,
Shown -CN, -CF ₃ or -OH, respectively. )

[0046]

[Chemical 16]

[0047]

[Chemical 17]

Among the disazo pigments, the compounds represented by the following formulas 18 and 19 are particularly preferable. These compounds have high sensitivity in the visible region, and when mixed in combination with a trisazo pigment, the stability of the pigment dispersion coating liquid is good and a good coating film can be formed.

[0049]

[Chemical 18]

[Chemical 19]

The photosensitive layer of the electrophotographic photosensitive member of the present invention can be of a dispersion type or a function separation type by combining a charge generating substance and a charge transporting substance. In the case of a dispersion type layer structure, a photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder is provided on a conductive substrate. In the case of the function separation type, a charge generation layer containing a charge generating substance and a binder is formed on a substrate, and a charge transporting layer containing a charge transporting substance and a binder is formed on the base. In that case, the charge generation layer and the charge transport layer may be laminated in reverse.
In the case of the function separation type, a charge transport material may be contained in the charge generation layer. Particularly, in the case of the positive charging structure, the sensitivity is good.

An intermediate layer may be provided between the photosensitive layer and the substrate in order to improve the adhesiveness and the charge blocking property. Further, in order to improve mechanical durability such as abrasion resistance, a protective layer may be provided on the photosensitive layer. As the binder used in the formation of the charge generation layer, the charge transport layer and the dispersion type photosensitive layer, any conventionally known binder having a good insulating property can be used, and there is no particular limitation. . 1
For example, polycarbonate (bisphenol A type, bisphenol Z type), polyester, methacrylic resin, acrylic resin, polyethylene, polyvinyl chloride, polyvinyl acetate, polystyrene, phenol resin,
Epoxy resin, polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl carbazole,
Polyvinyl butyral, polyvinyl formal, polyarylate, polyacrylamide, polyamide, phenoxy resin and the like are used. These binders can be used alone or as a mixture of two or more kinds.

When a photoconductor is prepared by using the above layer structure and materials, the film thickness and the ratio of the materials have preferable ranges. In the case of a negative charge type (lamination of substrate / charge generation layer / charge transport layer), the ratio of the charge generation substance to the binder in the charge generation layer is 20% by weight or more, and the film thickness is 0.01 to 5
μm is preferred. In the charge transport layer, the ratio of the charge transport material to the binder is preferably 20 to 200% by weight, and the film thickness is preferably 5 to 100 μm. Positively charged type (base /
In the case of the charge transport layer / charge generation layer stacking), the ratio of the charge transport material to the binder is 20 in the charge transport layer.
˜200 wt%, and the film thickness is preferably 5 to 100 μm. The charge generation layer preferably contains the charge generation substance in an amount of 20% by weight or more based on the binder. Furthermore, it is preferable to include a charge transporting substance in the charge generating layer, and by containing it, it is effective in suppressing the residual potential and improving the sensitivity. In this case, the charge transport material is preferably contained in the binder in an amount of 20 to 200% by weight.

In the case of a so-called dispersion type photoreceptor in which a charge generating substance and a charge transporting substance are dispersed in a binder resin, the binder resin is mixed in the photosensitive layer as the charge generating substance. The proportion of pigment is 5 to 95% by weight, and the film thickness is 10
100 μm is preferable. In that case, the ratio of the charge transport material to the binder resin is preferably 30 to 200% by weight.

Further, in these photosensitive layers, both dispersion type and function separation type, for the purpose of improving charging property and gas resistance,
So-called antioxidants such as phenol compounds, hydroquinone compounds, hindered phenol compounds, hindered amine compounds, and compounds in which hindered amine and hindered phenol are present in the same molecule can be added.

In the present invention, the conductive substrate has conductivity with a volume resistance of 10 ¹⁰ Ω · cm or less, for example, aluminum, nickel, chromium, nichrome, copper,
A metal such as silver, gold, or platinum, or a metal oxide such as indium oxide or tin oxide, copper iodide, or the like is coated on a film or a cylindrical drum, a belt-shaped film, paper, or the like by an evaporation or a sputtering method. Or plates, belts of aluminum, aluminum alloy, nickel, stainless steel, etc. I. , I. I. It is possible to use a raw pipe which has been subjected to a surface treatment by cutting superfinishing, polishing or the like after being made into a raw pipe by a method such as extrusion, drawing or the like. Also,
A conductive powder such as carbon black, indium oxide, or tin oxide may be dispersed in an appropriate resin and coated on plastic or the like.

As the charge transport substance used in the present invention, any known substance can be used. Specific examples thereof include the compounds shown in Table 17 having a basic structure represented by the following general formula 20 (JP-A-1-
No. 302260).

[0057]

[Chemical 20]

[0058]

[Table 17- (1)]

[0059]

[Table 17- (2)]

[0060]

[Table 17- (3)]

[0061]

[Table 17- (4)]

[0062]

[Table 17- (5)]

[0063]

[Table 17- (6)]

[0064]

[Table 17- (7)]

[0065]

[Table 17- (8)]

[0066]

[Table 17- (9)]

[0067]

[Table 17- (10)]

[0068]

[Table 17- (11)]

[0069]

[Table 17- (12)]

Other charge transport materials that can be used in the present invention include hole transport materials and electron transport materials. As the hole transport material, for example, the following general formula 2
The compounds as shown in 1-26, 28-31, 33 and 34 can be illustrated.

[0071]

[Chemical 21] [In the formula, R ¹ represents a methyl group, an ethyl group, a 2-hydroxyethyl group or a 2-chloroethyl group, R ² represents a methyl group, an ethyl group, a benzyl group or a phenyl group, and R ³ represents a hydrogen atom or chlorine. An atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a dialkylamino group or a nitro group. ]

[0072]

[Chemical formula 22] [In the formula, Ar is naphthalene, anthracene, styryl group and their substitution products or pyridines, furans,
Represents a thiophene, and R represents an alkyl group or a benzyl group. ]

[0073]

[Chemical formula 23] [In the formula, R ¹ represents an alkyl group, a benzyl group, a phenyl group, or a naphthyl group, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, or a dialkylamino group. It represents an aralkylamino group or a diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R ² may be the same or different. R ³ represents a hydrogen atom or a methoxy group. ]

[0074]

[Chemical formula 24] [In the formula, R ₁ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R ² and R ³ may be the same or different, a hydrogen atom and a carbon number.
1 to 4 represents an alkyl group, a hydroxyalkyl group, a chloroalkyl group or a substituted or unsubstituted aralkyl group, and R ² and R ³ may be bonded to each other to form a nitrogen-containing heterocycle. R ^{4 s} may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or halogen. ]

[0075]

[Chemical 25] [In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group or carbazolyl group. ]

[0076]

[Chemical formula 26] [In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and Ar is

[Chemical 27] R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom.
4 represents an alkoxy group or a dialkylamino group,
Is 1 or 2 and when n is 2, R ³ may be the same or different, R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted Represents a substituted benzyl group. ]

[0077]

[Chemical 28] [In the formula, R is a carbazolyl group, a pyridine group, a thienyl group, an indolyl group, a furyl group or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group or an anthryl group, and these substituents are dialkylamino groups,
Alkyl group, alkoxy group, carboxy group or ester thereof, halogen atom, cyano group, aralkylamino group,
It represents a group selected from the group consisting of N-alkyl-N-aralkylamino groups, amino groups, nitro groups and acetylamino groups. ]

[0078]

[Chemical 29] [In the formula, R ¹ represents a lower alkyl group, a benzyl group or a substituted or unsubstituted aryl group, and R ² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group or a lower alkyl group. Alternatively, it represents an amino group substituted with a benzyl group, and n represents an integer of 1 or 2. ]

[0079]

[Chemical 30] [In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ² and R ³ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, and R ⁴ represents It represents a hydrogen atom or a substituted or unsubstituted phenyl group, and Ar represents a phenyl group or a naphthyl group. ]

[0080]

[Chemical 31] [In the formula, n is an integer of 0 or 1, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group, and A
Is

[Chemical 32]9-anthryl group or substituted or unsubstituted N-alkyl group
Represents a rubazolyl group, where R^FourIs a hydrogen atom, alkyl
Group, alkoxy group, halogen atom Group, a substituted or unsubstituted aryl group, R^FiveAnd R⁶Is
May form a ring), m is an integer of 0, 1, 2 or 3
Yes, R when m is 2 or more^FourCan be the same or different
Yes. ]

[0081]

[Chemical 33] [In the formula, R ¹ , R ² and R ³ are a hydrogen atom, a lower alkyl group,
It represents a lower alkoxy group, a dialkylamino group or a halogen atom, and n represents 0 or 1. ]

[0082]

[Chemical 34] [In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ² and R ³ may be the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. ]

The compound represented by the general formula 21 is, for example, 9-ethylcarbazole-3-aldehyde-1-methyl-1-
Examples thereof include phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone. Further, the compound represented by the general formula 22 is
For example, 4-diethylaminostyrene-β-aldehyde-1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-
Aldehyde-1-benzyl-1-phenylhydrazone and the like.

Examples of the compound represented by the general formula 23 include 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldevid-1-benzyl-1-phenylhydrazone, 4-diethylamino. Benzaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1-benzyl-1- (4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde -1,1-diphenylhydrazone, etc. Examples of the compound represented by the general formula 24 include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-
Dibenzylaminophenyl) propane, 2,2'-dimethyl-
Examples include 4,4'-bis (diethylamino) -triphenylmethane.

The compound represented by the general formula 25 includes, for example, 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene. In addition, the compound represented by the general formula 26
For example, 9- (4-dimethylaminobenzylidene) fluorene,
3- (9-fluorenylidene) -9-ethylcarbazole and the like.

Examples of the compound represented by the general formula 28 include 1,2-bis (4-diethylaminostyryl) benzene, 1,2
There is 2-bis (2,4-dimethoxystyryl) benzene. In addition, examples of the compound represented by the general formula 29 include 3-styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.

Examples of the compound represented by the general formula 30 include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4 -Diethylaminostyryl) naphthylene etc. Examples of the compound represented by the general formula 31 include 4'-diphenylamino-
α-Phenylstilbene, 4'-Methylphenylamino-α
-For example, phenyl stilbene.

Examples of the compound represented by the general formula 33 include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-
Diethylaminophenyl) pyrazoline, 1-phenyl-3- (4
-Dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazoline and the like. The compound represented by the general formula 34 includes N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-bisphenyl] -4,4′-diamine, N, N′-diphenyl-N, N′-bis (chlorophenyl)-
Examples include [1,1′-biphenyl] -4,4′-diamine and 3,3′-dimethylbenzidine.

Other hole transport materials include, for example, 2,
5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2,5-bis [4- (4-diethylaminostyryl) phenyl] -1,3,4-oxydiazole, 2- ( Oxadiazole compounds such as 9-ethylcarbazolyl-3-)-5- (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-vinyl-4
There are low-molecular compounds such as oxazole compounds such as-(2-chlorophenyl) -5- (4-diethylaminophenyl) oxazole and 2- (4-diethylaminophenyl) -4-phenyloxazole. Further, polymer compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, pyreneformaldehyde resin, ethylcarbazoleformaldehyde resin can also be used.

Examples of the electron transport material include chloranil, bromanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone. , 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Examples include trinitro-4H-indeno [1,2-b] thiophen-4-one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide.

The photoconductive composition of the present invention can be applied to a solar cell, an optical sensor, an optical switching element, etc. in addition to the electrophotographic photoreceptor.

[0092]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereby.

Specific examples of the pigments used in the examples are No. Is
The following azo structural component No. And the coupler Nos. In Tables 1 to 16. The pigments are indicated by the combination of the respective numbers. In the disazo pigment, when different couplers are bonded on the left and right, both are listed.

[0094]

[Chemical 35]

[0095]

[Chemical 36]

[0096]

[Chemical 37]

[0097]

[Chemical 38]

[0098]

[Chemical Formula 39]

[0099]

[Chemical 40]

[0100]

[Chemical 41]

[0101]

[Chemical 42]

Example 1-1 Disazo compound (Specific example No. II-17) 0.012 g Trisazo compound (Specific example No. I-70) 0.238 g Polyvinyl butyral resin (XYHL manufactured by UCC) cyclohexanone 1% Solution 4.75 g Cyclohexanone 7 g was put in a 50 cc glass container together with 5 mmφ PZT balls, ball milled for 5 days, methyl ethyl ketone (MEK) was added, and ball milling was further performed for 1 day to prepare a CGL coating solution. did.

The above CGL coating liquid was applied onto a 75 μm polyester film vapor-deposited on aluminum with a blade having a gap of 30 μm, and then dried by heating at 80 ° C. for 2 minutes to form CGL.

Next, a CTL coating liquid having the following composition was prepared,
After applying a blade coating on the CGL, heat-dry at 80 ° C., and further heat-dry at 130 ° C. for 5 minutes to about 20 μm.
A CTL film of m was formed to prepare a photoconductor.

[CTL coating liquid] Z-type polycarbonate resin (number average molecular weight of about 50,000) 10 g α-phenylstilbene compound (1) 8 g toluene 72 g represented by the following chemical structural formula 43

Α-Phenylstilbene compound (1)

[Chemical 43]

Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-1
1-2 A photoreceptor was prepared in the same manner as in Example 1-1, except that the contents of the disazo compound and the trisazo compound in the CGL coating liquid of Example 1-1 were changed as shown in Table 18.

[0108]

[Table 18]

(Evaluation) Examples 1-1 to 1-5 and Comparative Example 1
After charging the photoconductors prepared in -1 to 1-2 with the electrostatic characteristic measuring device EPA8100 manufactured by Kawaguchi Electric Co., Ltd. at -5.5 Kv for 2 seconds to charge potential V ₂ and the photoconductor to 800 volt, Light from a 2856K tungsten lamp is 78
Photosensitivity was measured by irradiation through a bandpass filter of 0 nm (half-value width of 20 nm). The results are shown in Table 19. In the table, E1 / 10 (μJ / cm ² ) has a surface potential of 800.
It represents the amount of light required to attenuate from v to 80v.
(That is, the smaller the value of E1 / 10, the higher the sensitivity.)

[0110]

[Table 19]

From Table 19, it can be seen that the mixed systems of Examples 1-1 to 1-5 have a smaller E1 / 10 and are sensitized as compared with the single systems of Comparative Examples 1-1 and 1-2. .

Examples 1-6 to 1-9 The disazo compounds of Example 1-3 were each prepared as a specific example.
II-29, No. II-19, No. II-12, No. II
A photoconductor was prepared in the same manner as in Example 1-3, except that the compound was changed to -200, and the charging potentials V ₂ and E 1/10 were measured in the same manner as in Example 1-1. The results are shown in Table 20.

Examples 1-10 to 1-13 The trisazo compounds of Examples 1-3 are each used as a specific example N.
o. I-72, No. I-67, No. I-214, N
o. A photoconductor was prepared in the same manner as in Example 1-3, except that the compound of I-77 was used. The charging potential V ₂ and E 1/10 were measured in the same manner as in Example 1-1. The results are shown in Table 20.

[0114]

[Table 20]

Comparative Examples 1-3 to 1-6 The trisazo compound of Comparative Example 1-1 was used as a specific example N.
o. I-72, No. I-67, No. I-214, N
o. A photoreceptor was prepared in the same manner as in Comparative Example 1-1, except that the compound of I-77 was used. The charging potential V ₂ and E 1/10 were measured in the same manner as in Example 1-1. The results are shown in Table 21.

Comparative Example 1-7 A photoconductor was prepared in the same manner as in Example 1-1, except that the perylene compound represented by the following formula 44 was used instead of the disazo compound in Example 1-2. As well as charging potentials V ₂ and E 1
/ 10 was measured. The results are shown in Table 21.

Perylene compound

[Chemical 44]

[0118]

[Table 21]

It can be seen from Tables 20 and 21 that the sensitivity was significantly sensitized when the trisazo compound was mixed with the disazo compound as compared with when the trisazo compound was used alone. More specifically, Examples 1-6 to 1-9 are the trisazo compound Nos. This is an example of the combination of I-70 and various disazo compounds. It can be seen that the sensitivity is higher than that of Comparative Example 1-1 of I-70 alone. In addition, Examples 1-10 to 1-13 are the trisazo compound Nos. I-
72, No. I-67, No. I-214, No. I-7
7 is a mixed example of a disazo compound, it can be seen that the sensitivity of the former is about twice as high as that of Comparative examples 1-3 to 1-6 in the case of using each trisazo compound alone. In addition, when a perylene compound and a trisazo compound, which have only a sensitizing effect when mixed with a phthalocyanine compound, do not have a sensitizing effect, but rather the sensitivity decreases.

Examples 1-14 to 1-17 The disazo compounds of Example 1-3 were each used as a specific example.
II-17.18, No. II-17.19, No. II-1
7/24, No. A photoreceptor was prepared in the same manner as in Example 1-3, except that the compound of II-200 was used, and the charging potential V ₂ and E 1/10 were measured in the same manner. The results are shown in Table 22.

Examples 1-18 to 1-19 The specific examples of the disazo compounds of Example 1-12 are shown below.
o. II-17 / 24, No. A photoconductor was prepared in the same manner as in Example 1-12 except that the compound of II-200 was used, and the charging potential V ₂ and E 1/10 were measured in the same manner. The results are shown in Table 22.

[0122]

[Table 22]

In Examples 1-14 to 1-17, the trisazo compound No. This is an example of a mixed system of I-70 and various disazo compounds, and Examples 1-18 to 1-19 show trisazo compound No. This is an example of a mixed system of I-214 and various disazo compounds. The former is Comparative Example 1-1 and the latter is Comparative Example 1.
By comparing with -5, the sensitizing effect of the mixed system becomes clear.

Further, in order to investigate the gas resistance of the photoconductor of the present invention, the photoconductors produced in the above-mentioned Examples and Comparative Examples were tested for 5 p.
Example 1 after exposure to a pm NO gas atmosphere for 5 days
V ₂ and E 1/10 were measured in the same manner as in -1. The results are shown in Table 2.
3 and Table 24.

[0125]

[Table 23- (1)]

[0126]

[Table 23- (2)]

[0127]

[Table 24]

From Tables 23 and 24, it can be seen that when the trisazo pigment and the disazo pigment are mixed, the charging potential is less lowered by gas exposure and the sensitivity is less changed than when the trisazo pigment is used alone.

Example 1-20 In Example 1-3, except that the charge transport material was changed from the α-phenylstilbene compound (1) to the α-phenylstilbene compound (2) represented by the following chemical structural formula 45. A photoconductor was prepared in the same manner as in Example 1-3.

Α-Phenylstilbene compound (2)

[Chemical formula 45]

Comparative Example 1-8 The same procedure as in Comparative Example 1-1 except that the charge transporting material in Comparative Example 1-1 was changed from α-phenylstilbene compound (1) to α-phenylstilbene compound (2). To produce a photoconductor.

Example 1-21 In Example 1-3, except that the charge transporting material was changed from the α-phenylstilbene compound (1) to the hydrazone compound represented by the following chemical structural formula 46 in Example 1-3.
A photoconductor was prepared in the same manner as in 3.

[0133]

[Chemical formula 46]

Comparative Example 1-9 In Comparative Example 1-1, the charge transporting material was changed from the α-phenylstilbene compound (1) to the hydrazone compound represented by the chemical formula 46 used in Example 1-21. A photoconductor was prepared in the same manner as in Comparative Example 1-1.

(Evaluation) The results of evaluation of the photoreceptors of Examples 1-20 to 1-21 and Comparative Examples 1-8 to 1-9 in the same manner as in Example 1-1 are shown in Table 25.

[0136]

[Table 25]

Example 1-22 Disazo Compound (Specific Example No. II-17) 1.25 g Trisazo Compound (Specific Example No. I-70) 1.25 g Cyclohexanone 30 g was placed in a glass pot container containing agate balls. Ball milling was performed for 3 days to prepare a mixed pigment liquid A.

Next, a photosensitive layer coating liquid having the following composition was prepared. Polycarbonate resin (C-1400 manufactured by Teijin Chemicals Ltd.) 5 g α-phenyl stilbene compound (I) represented by chemical structural formula 43 5 g 2,5 ditertiarybutyl hydroquinone 0.05 g Mixed pigment liquid A 15 g THF 30 g

After coating the above-mentioned photosensitive layer coating liquid with a doctor blade having a gap of 250 μm on an aluminum vapor-deposited polyester film coated with an alcohol-soluble polyamide resin (Alamine CM8000 manufactured by Toray Co., Ltd.) as an intermediate layer in a thickness of 0.3 μm , Heat dry at 80 ℃ for 5 minutes, then 1
It was heated and dried at 20 for 1 hour to form a photosensitive layer film having a thickness of about 20 μm to prepare a photoreceptor.

The obtained photoreceptor was evaluated in the same manner as in Example 1-1. V ₂ = 850v, E 1/10 = 0.
It was 68 (μJ / cm ² ). (However, the charging condition is +
Charging was performed at 5.5 kv. )

Comparative Example 1-10 Trisazo Compound (Specific Example No. I-70) 2.5 g Cyclohexanone 30 g was placed in a glass pot container containing agate balls and ball milled for 3 days to prepare a mixed pigment liquid.

Next, a photosensitive layer coating liquid having the following composition was prepared. Polycarbonate resin (C-1400 manufactured by Teijin Chemicals Ltd.) 5 g α-phenyl stilbene compound (1) represented by chemical structural formula 43 5 g 2,5 ditertiary butyl hydroquinone 0.05 g The above mixed pigment liquid 15 g THF 30 g

Alcohol-soluble polyamide resin (Alamine CM8000 manufactured by Toray Industries, Inc.) was coated as an intermediate layer on an aluminum vapor-deposited polyester film having a thickness of 0.3 μm, and the photosensitive layer coating solution was coated with a doctor blade, followed by heating at 80 ° C. for 5 minutes. Dry, then heat dry at 120 for 1 hour
A photosensitive layer film having a thickness of μm was formed to prepare a photoconductor.

The obtained photoreceptor was evaluated in the same manner as in Example 1. As a result, V ₂ = 900v, E 1/10 = 1.50.
(ΜJ / cm ² ). (However, the charging condition is +5.
Ten charges were performed at 5 kv. )

Further, in order to examine the gas resistance of the photoreceptor of the present invention, Examples 1-20 to 1-22 and Comparative Examples 1-8 to
After exposing the photoreceptor prepared in 1-10 to 5 ppm NO gas atmosphere for 5 days, V ₂ was applied in the same manner as in Example 1-1.
And E1 / 10 were measured. The results are shown in Table 26.

[0146]

[Table 26]

From Table 26, in the case where the trisazo pigment and the disazo pigment were mixed,
It can be seen that there is little decrease in the charging potential due to gas exposure and little change in sensitivity.

Example 1-23 In each of Examples 1-1 to 1-22, the disazo pigment and the trisazo pigment were mixed and pulverized at the same time, but this time, the disazo pigment and the trisazo pigment were separately separated. The dispersion liquid dispersed in was mixed simply later. That is, the PSZ balls 100 in 5 mm are separately prepared from the following composition liquids.
After putting it in a 50 cc glass container containing g and performing ball milling for 5 days, methyl ethyl ketone was added,
Further, ball milling was performed for 1 day to prepare dispersions A and B.

[Dispersion A] Disazo Compound (Specific Example No. II-17) 0.25 g Polyvinyl butyral resin (XYHL, XYHL) 1% cyclohexanone solution 4.75 g Cyclohexanone 7 g [Dispersion B] Trisazo compound ( Specific example No. I-70) 0.25 g Cyclohexanone 1% solution of polyvinyl butyral resin (XYHL manufactured by UCC) 4.75 g Cyclohexanone 7 g

Subsequently, [dispersion liquid A] and [dispersion liquid B] were mixed in equal amounts to prepare a CGL liquid. Next, a laminated photoreceptor was prepared in the same manner as in Example 1-1, except that this CGL solution was used. Further, the obtained photoconductor was exposed to a 5 ppm NO gas atmosphere for 5 days to evaluate gas resistance. The chargeability and sensitivity before and after exposure to NO gas were measured in the same manner as in Example 1-1. The results are shown in Table 27. (For comparison, the results of Comparative Example 1-1 are also shown in the table.)

[0151]

[Table 27]

From Table 27, using the azo pigment mixture,
As compared with Comparative Example 1-1 using CGL containing only the trisazo pigment, it is found that the sensitivity is less decreased and the gas resistance is excellent.

Examples 1-24 to 1-30 In place of the disazo pigment used in Example 1-3, specific examples Nos. II-1, No. II-6, No. II-8, No.
II-20, No. II-28, No. II-31, No. II
A photoconductor was prepared in the same manner as in Example 3 except that -40 was used and the CTL film was applied to a thickness of 30 μm. In the same manner as in Example 1-1, the charging potentials V ₂ and E1 /
Table 28 shows the results of measuring 10.

[0154]

[Table 28]

From Table 28, the sensitizing effect of the mixed system of the present invention becomes clear.

Example 2-1 Trisazo Pigment (Specific Example No. I-70) 0.19 g Disazo Pigment (Specific Example No. III-60) 0.01 g Polyvinyl butyral resin (XYHL: manufactured by UCC) cyclohexanone 2 parts by weight % Solution 4.0 g The above composition was placed in a 50 cc glass container half filled with 5 mm diameter PSZ balls by volume and ball-milled for 7 days. After that, 6.0 g of cyclohexanone was added and ball milling was performed for 3 days, and then 13.0 g of cyclohexanone was added and ball milling was performed for 1 day to prepare a charge generation layer coating solution.

The charge generation layer coating solution described above was applied to a thickness of 0.2 m.
m aluminum plate (JIS 1080) with a doctor blade having a gap of 50 μm, and then 120
After drying at 10 ° C. for 10 minutes, a charge generation layer having a thickness of about 0.2 μm was formed.

Next, a charge transport layer coating solution prepared by stirring and dissolving the following compounds was applied onto the charge generating layer with a doctor blade and dried at 120 ° C. for 20 minutes to give a thickness of about 28 μm. The charge generation layer of was formed to prepare a photoconductor.

[Composition of Coating Liquid for Charge Transport Layer] 9 parts by weight of α-phenylstilbene compound (1) represented by the structural formula 43: 10 parts by weight of bisphenol Z-type polycarbonate resin (TS2050; manufactured by Teijin Chemical: viscosity average) (Molecular weight 40,000)

Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-1
2-2 Photosensitization was performed in the same manner as in Example 2-1, except that the contents of the trisazo pigment [I] and the disazo pigment [III] in the charge generation layer coating liquid of Example 2-1 were changed as shown in Table 29. The body was made.

[0161]

[Table 29]

Examples 2-1 to 2-5, Comparative examples 2-1 to 2
The electrophotographic characteristic measuring device EPA
8100 (Kawaguchi Electric Co., Ltd.) in dynamic mode,-
Charge potential V ₂ when charged at 6 kV for 2 seconds and -800 V on the photoconductor, and then measure the photosensitivity by irradiating the light of a tungsten lamp with a color temperature of 2856K through a bandpass filter of 780 nm (half-value width 13 nm). did.
The results are shown in Table 30.

The photosensitivity S (V · cm ² / μJ) is
The exposure amount required to attenuate the surface potential from −800 V to −100 V is E (μJ / cm ² ), and S = 700 /
It is obtained from E, and it is determined that the larger the value of S is, the higher the sensitivity is.

[0164]

[Table 30]

From Table 30, it can be seen that the mixed systems of Examples 2-1 to 2-5 have higher photosensitivity and are sensitized than the single systems of Comparative Examples 2-1 to 2-2.

Next, in order to examine the gas resistance of the photoconductor of the present invention, the photoconductors prepared in Examples 2-1 to 2-5 and Comparative examples 2-1 to 2-2 were subjected to 10 ppm ozone gas at 10 ppm. After exposure for a day, the charging potential V ₂ and the photosensitivity S were measured in the same manner as in Example 2-1. The results are shown in Table 31.

[0166]

From Table 31, it can be seen that the disazo pigment [III] alone causes less decrease in the charging potential due to ozone exposure than the trisazo pigment [I] alone. Further, it can be seen that the mixture of the trisazo pigment [I] and the disazo pigment [III] causes less decrease in the charging potential due to ozone exposure and less change in sensitivity than the case of using the trisazo pigment [I] alone.

Examples 2-6 to 2-9 The trisazo pigments [I] of Example 2-3 were respectively used as specific examples No. I-205, No. I-88, No. I-21
4, No. Example 2 except that the compound of I-67 was changed.
A photoconductor was prepared in the same manner as in -3.

Examples 2-10 to 2-13 The disazo pigments [III] of Example 2-3 were respectively prepared according to the specific example Nos. III-1, No. III-201, No. III-2
17, No. A photoconductor was prepared in the same manner as in Example 2-3, except that the compound of III-233 was used instead.

Comparative Examples 2-3 to 2-6 Each of the trisazo pigments [I] of Comparative Example 2-1 was used as a specific example. I-205, No. I-88, No. I-21
4, No. Comparative Example 2 except that the compound of I-67 was used instead.
A photoconductor was prepared in the same manner as in -1.

Example 2-14 In the same manner as in Example 2-3 except that the charge transporting material of Example 2-3 was changed to the α-phenylstilbene compound (2) represented by the structural formula 45. A photoconductor was prepared.

Example 2-15 Example 2 except that the hydrazone compound represented by the structural formula 46 was used instead of the charge transport material of Example 2-3.
A photoconductor was prepared in the same manner as in Example 3, and the charging potential V ₂ and the photosensitivity S were measured in the same manner as in Example 2-1.

Examples 2-6 to 2-15 and Comparative Example 2-3
Table 31 shows the measurement results of the charging potential V ₂ and the photosensitivity S including the gas resistance test for the photoconductors obtained in Examples ₂ to 6 below.

[0175]

[Table 31]

From Table 31, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

Example 3-1 In Example 2-3, the disazo pigment was used as a specific example. I
A photoconductor was prepared in the same manner as in Example 2-3, except that V-1 was used.

With respect to the obtained photoreceptor, the charging potential V ₂ and the photosensitivity S including the gas resistance test were measured in the same manner as in Example 2-1. The results are shown in Table 32.

[0179]

[Table 32] ┻━━━━┛

Examples 3-2 to 3-5 The trisazo pigments [I] of Example 3-1 were prepared according to the specific example Nos. I-205, No. I-88, No. I-21
4, No. Example 3 except that the compound of I-67 was changed.
A photoconductor was prepared in the same manner as in -1.

Examples 3-6 to 3-9 The disazo pigments [IV] of Example 3-1 were prepared according to the specific example Nos. IV-4, No. IV-19, No. IV-2
5, No. A photoconductor was prepared in the same manner as in Example 3-1 except that the compound of IV-30 was used.

Example 3-10 In Example 2-14, the disazo pigment was used as a specific example.
A photoconductor was prepared in the same manner as in Example 2-14, except that IV-1 was used.

Example 3-11 In Example 2-15, the disazo pigment was used as a specific example.
A photoconductor was prepared in the same manner as in Example 2-15, except that IV-1 was used.

Table 33 shows the measurement results of the charging potential V ₂ and the photosensitivity S including the gas resistance test for the photoconductors obtained in Examples 3-2 to 3-11.

[0185]

[Table 33]

From Table 33, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

Example 4-1 In Example 2-3, the disazo pigment was used as a specific example. V
A photoconductor was prepared in the same manner as in Example 2-3, except that the photosensitive member was changed to -17.

With respect to the obtained photoconductor, the charging potential V ₂ and the photosensitivity S including the gas resistance test were measured in the same manner as in Example 2-1. The results are shown in Table 34.

[0189]

[Table 34] ┻━━━━┛

Examples 4-2 to 4-5 The trisazo pigments [I] of Example 4-1 were each used as a specific example. I-205, No. I-88, No. I-21
4, No. Example 4 except that the compound of I-67 was changed.
A photoconductor was prepared in the same manner as in -1.

Examples 4-6 to 4-9 The disazo pigments [V] of Example 4-1 were prepared according to specific examples Nos. V-11, No. V-14, No. V-23, N
o. A photoreceptor was prepared in the same manner as in Example 4-1, except that the compound of V-60 was used.

Example 4-10 In Example 2-14, the disazo pigment was used as a specific example.
A photoconductor was prepared in the same manner as in Example 2-14, except that V-17 was used.

Example 4-11 In Example 2-15, the disazo pigment was used in the specific example No.
A photoconductor was produced in the same manner as in Example 2-15, except that V-17 was used.

Table 35 shows the measurement results of the charging potential V ₂ and the photosensitivity S of the photoconductors obtained in Examples 4-2 to 4-11, including the gas resistance test.

[0195]

[Table 35]

From Table 35, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

Example 5-1 In Example 2-3, the disazo pigment was used as a specific example. V
A photoconductor was prepared in the same manner as in Example 2-3, except that I-63 was used.

With respect to the obtained photoreceptor, the charging potential V ₂ and the photosensitivity S including the gas resistance test were measured in the same manner as in Example 2-1. The results are shown in Table 36.

[0199]

[Table 36] ┻━━━━┛

Examples 5-2 to 5-5 The trisazo pigment [I] of Example 5-1 was used as a specific example. I-205, No. I-88, No. I-21
4, No. Example 5 except that the compound of I-67 was changed.
A photoconductor was prepared in the same manner as in -1.

Examples 5-6 to 5-9 Each of the disazo pigments [VI] of Example 5-1 was prepared according to the specific example Nos. VI-1, No. VI-64, No. VI-2
23, No. A photoconductor was prepared in the same manner as in Example 5-1 except that the compound of VI-224 was used.

Example 5-10 In Example 2-14, the disazo pigment was used as a specific example.
A photoconductor was prepared in the same manner as in Example 2-14, except that VI-63 was used.

Example 5-11 In Example 2-15, the disazo pigment was prepared according to the specific example No.
A photoconductor was produced in the same manner as in Example 2-15 except that VI-63 was used.

Table 37 shows the measurement results of the charging potential V ₂ and the photosensitivity S of the photoconductors obtained in Examples 5-2 to 5-11 including the gas resistance test.

[0205]

[Table 37]

From Table 37, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

Example 6-1 In Example 2-3, the disazo pigment was used as a specific example No. V
A photoconductor was prepared in the same manner as in Example 2-3, except that II-1 (R ⁴ = CN) was used.

With respect to the obtained photoreceptor, the charging potential V ₂ and the photosensitivity S including the gas resistance test were measured in the same manner as in Example 2-1. The results are shown in Table 38.

[0209]

[Table 36] ┻━━━━┛

Examples 6-2 to 6-5 The trisazo pigment [I] of Example 6-1 was used as a specific example. I-205, No. I-88, No. I-21
4, No. Example 6 except that the compound of I-67 was changed.
A photoconductor was prepared in the same manner as in -1.

Examples 6-6 to 6-9 The disazo pigments [VII] of Example 6-1 were prepared according to the specific example Nos. VII-89 (R ⁴ = CN), No. VII-19
(R ⁴ = CN), No. VII-19 (R ⁴ = Cl), N
o. A photoconductor was prepared in the same manner as in Example 6-1 except that the compound was VII-19 (R ⁴ = Br).

Example 6-10 In Example 2-14, the disazo pigment was used as a specific example.
Example 2-1 except that it was changed to VII-1 (R ⁴ = CN).
A photoconductor was prepared in the same manner as in 4.

Example 6-11 In Example 2-15, the disazo pigment was used as a specific example No.
Example 2-1 except that it was changed to VII-1 (R ⁴ = CN).
A photoconductor was prepared in the same manner as in 5.

Table 39 shows the measurement results of the charging potential V ₂ and the photosensitivity S of the photoconductors obtained in Examples 6-2 to 6-11 including the gas resistance test.

[0215]

[Table 39]

From Table 39, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

Example 7-1 In Example 2-3, the disazo pigment was used as a specific example. V
A photoconductor was prepared in the same manner as in Example 2-3, except that III-195 was used.

With respect to the obtained photoreceptor, the charging potential V ₂ and the photosensitivity S including the gas resistance test were measured in the same manner as in Example 2-1. The results are shown in Table 40.

[0219]

[Table 40] ┻━━━━┛

Examples 7-2 to 7-5 The trisazo pigments [I] of Example 7-1 were each used as a specific example. I-205, No. I-88, No. I-21
4, No. Example 7 except that the compound was I-67.
A photoconductor was prepared in the same manner as in -1.

Examples 7-6 to 7-9 The disazo pigments [VIII] of Example 7-1 were prepared according to the specific example Nos. VIII-1, 195, No. VIII-1, N
o. VIII-191, No. A photoconductor was prepared in the same manner as in Example 7-1, except that the compound of VIII-17 was used.

Example 7-10 In Example 2-14, the disazo pigment was used as a specific example.
A photoconductor was prepared in the same manner as in Example 2-14, except that VIII-195 was used.

Example 7-11 In Example 2-15, the disazo pigment was prepared according to the specific example No.
A photoconductor was prepared in the same manner as in Example 2-15, except that VIII-195 was used.

Table 41 shows the measurement results of the charging potential V ₂ and the photosensitivity S of the photoreceptors obtained in Examples 7-2 to 7-11 including the gas resistance test.

[0225]

[Table 41]

From Table 41, the photoconductive composition of the present invention is
It can be seen that the photosensitivity is excellent, and the decrease in charging potential and the change in sensitivity due to gas exposure are small.

[0227]

The photoconductive composition according to claim 1 is composed of a mixture of a specific disazo pigment and a specific trisazo pigment. The electrophotographic photosensitive member does not decrease the sensitivity to visible light and has less deterioration in charging characteristics due to ozone or NOx gas.

Since the electrophotographic photoreceptor of claim 4 contains the simultaneous pulverized mixture of the trisazo pigment and the dispigment, it has high sensitivity to visible light and near infrared light. Have.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical indication location G03G 5/06 360 C 9221-2H 367 9221-2H (72) Inventor Tomoyuki Shimada 1 chome Magome, Ota-ku, Tokyo No. 3-6 In Ricoh Co., Ltd. (72) Inventor Mitsuru Hashimoto 1-3-6 Nakamagome, Ota-ku, Tokyo In Ricoh Co., Ltd.

Claims (4)

[Claims] 1. A photoconductive composition comprising one or more trisazo pigments represented by the following general formula 1 and one or more disazo pigments represented by the following general formulas 2 to 8. . [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] (However, in the above general formulas 1 to 8, A, B and D
Represents a coupler residue and may be the same or different, and R ^{1 to} R ⁷ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group and may be the same or different. ) 2. An electrophotographic photoreceptor comprising a photoconductive layer formed on a conductive support, wherein one or more trisazo pigments represented by the following general formula 1 and 1 are contained in the photoconductive layer. An electrophotographic photoreceptor containing at least one of the disazo pigments represented by the following general formulas 2 to 8. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] (However, in the above general formulas 1 to 8, A, B and D
Represents a coupler residue and may be the same or different, and R ^{1 to} R ⁷ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group and may be the same or different. ) 3. The coupling residue A, B and D in the general formulas 1 to 8 is an azo pigment selected from the residues represented by the following general formulas 9 to 14. Electrophotographic photoreceptor. [Chemical 9] [However, in the above formula, X ¹ , Y ¹ and Z respectively represent the following. ^{X 1: -OH, -N (R} 8) (R 9) or, -NHSO ₂ -
R ¹⁰ . (R ⁸ and R ⁹ represent a hydrogen atom, an acyl group or a substituted or unsubstituted alkyl group, and R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) Y ¹ : hydrogen atom A halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxy group, a sulfone group, a benzimidazolyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted allofanoyl group or -CON (R ¹¹ ) (Y ² ) Is represented. {R ¹¹ represents a hydrogen atom, an alkyl group or a substituted product thereof, or a phenyl group or a substituted product thereof, and Y ² is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, or -N = C (R ¹² ) (R ¹³ ) (wherein R ¹² is a hydrocarbon ring group or a substituted product thereof, a heterocyclic group or a substituted product thereof, a styryl group or a substituted product thereof, and R ¹³ is a hydrogen atom, an alkyl group or a substituted product thereof, or phenyl Represents a group or a substituent thereof, or R ¹² and R ¹³ may form a ring together with the carbon atom bonded to them. } Z: Hydrocarbon ring group or a substituted body thereof, or heterocyclic group or a substituted body thereof. ] [Chemical 10] (In the above formula, R ¹⁴ represents a substituted or unsubstituted hydrocarbon group.) (In the above formula, R ¹⁵ represents a substituted or unsubstituted hydrocarbon group.) (In the above formula, R ¹⁶ represents an alkyl group, a carbamoyl group, a carboxyl group or an ester thereof, and Ar represents a substituted or unsubstituted aromatic hydrocarbon group.) (In the above formula, X ² represents a divalent group of an aromatic hydrocarbon or a divalent group of a heterocycle.) (In the above formula, X ² represents an aromatic hydrocarbon divalent group or a heterocyclic divalent group.) 4. The photoconductor for electrophotography according to claim 2, which contains a mixture of the trisazo pigment and the disazo pigment simultaneously pulverized.