JPH02230253A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body which has a high sensitivity, high potential stability in repetitive use, small residual potential and high durability by incorporating a phthalocyanine pigment and specific compds. into a photoconductive layer. CONSTITUTION:The photoconductive layer contains the phthalocyanine pigment and at least one kind of the compds. expressed by formula I or formula III or formula III. In the formulas I to III, Z denotes a sulfur atom or oxygen atom; R1 denotes an alkyl group, alkoxy group, etc.; R2 and R3 respective denote a hydrogen atom, alkyl group, etc.; R4 denotes a methylene group, polymethylene group, etc. R1 and R2 or R2 and R3 may be respectively connected. The monovalent group of R1 to R3 and the bivalent group of R4 may be substd. or unsubstd. The electrophotographic sensitive body having the high sensitivity, the high potential stability in repetitive use, the small residual potential and the high durability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an electrophotographic photoreceptor having a photoconductive layer provided on a conductive support. ``Prior Art'' Electrophotographic photoreceptors that are sensitive to visible light have been developed for application in copying machines, optical printers, etc. Conventionally, such electrophotographic photoreceptors include selenium, zinc oxide,
Photoreceptors based on inorganic photoconductive materials such as sulfide dominium have been widely used. However, such inorganic photoreceptors do not necessarily satisfy the performance required as electrophotographic photoreceptors for copying machines and the like, such as photosensitivity, thermal stability, moisture resistance, and durability. For example, selenium photoreceptors crystallize due to heat or fingerprint stains when touched, so the above-mentioned characteristics required for electrophotographic photoreceptors tend to deteriorate. Further, electrophotographic photoreceptors using sulfurized dominium have poor moisture resistance and durability, and electrophotographic photoreceptors using zinc oxide have problems with durability such as film strength.

Furthermore, since selenium and cadmium sulfide are toxic, there are significant restrictions in manufacturing and handling.

In recent years, in order to eliminate the drawbacks of photoreceptors using these inorganic materials, electrophotographic photoreceptors using various organic materials have been researched and developed, and some of them have been put into practical use. For example, an electrophotographic photoreceptor (US Pat. No. 3,484,237) consisting of boly N-vinylcarhazole and 2,4.7-}linitrofluoren-9-one; Sensitized with salt-based dyes (Special Publications 1977-
No. 25658), an electrophotographic photoreceptor whose main component is an am content (Japanese Patent Application Laid-Open No. 47-37543), an electrophotographic photoreceptor whose main component is a eutectic complex consisting of a dye and a resin (Japanese Patent Application Laid-open No. 47-37543),
-10785) etc. However, although these photoreceptors have improved to some extent the drawbacks of the inorganic photoreceptors,
Generally, they had low photosensitivity, were not suitable for repeated use, and did not fully meet the requirements for electrophotographic photoreceptors. In order to improve these shortcomings, an electrophotographic photoreceptor with a functionally separated photoconductive layer in which the charge generation function and charge transport function are assigned to different materials was proposed, and it has become the mainstream of current research. It has become.

Functionally separated electrophotographic photoreceptors expand the range of material selection,
Along with this, it is possible to improve the characteristics of electrophotographic photoreceptors such as sensitivity and durability, and it also has the advantage of being able to select materials from a wide range that are convenient for forming coatings on electrophotographic photoreceptors. Various organic dyes and 4M pigments have been developed as effective organic charge generating substances for use in the charge generating layer of such functionally separated electrophotographic photoreceptors, such as azo pigments with various structures, perylene pigments, etc. Pigments, polycyclic quinone pigments, square methine dyes, etc. are used.

However, these pigments show relatively good sensitivity in the short or medium wavelength range, but have low sensitivity in the long wavelength range, and are used in laser printers, etc. that use semiconductor laser light sources that are expected to have high reliability. That was difficult. The oscillation wavelength of potassium-aluminum-arsenic light-emitting atoms, which are currently widely used as semiconductor lasers, is 750.
It is more than nm. "The secret problem that the invention seeks to solve" It is known that phthalocyanine compounds, which are one of the organic photoconductive materials, have a sensitivity range that extends to longer wavelengths than the pigments, dyes, etc. mentioned above. However, it seems to be lacking in electrophotographic properties such as sensitivity and chargeability.

In order to improve these drawbacks, phthalocyanines with various changes in the central metal or various crystal forms have been developed. Various crystalline forms of phthalocyanine have been discovered through the process of converting unstable α-type phthalocyanine into stable β-type crystalline form. For example, ε-1 type copper phthalocyanine, X-type metal-free phthalocyanine, and m-type titanyl phthalocyanine are known. Although these phthalocyanines have sensitivity in the long wavelength range, they are insufficiently sensitive for use in copiers or optical printers, and also have drawbacks such as insufficient potential stability or large residual potential when used repeatedly. However, it could not be put to practical use. On the other hand, methods for improving the sensitivity of electrophotographic photoreceptors containing phthalocyanine pigments include adding charge-transporting compounds such as hydrazone compounds and oxazole compounds, or adding electron-withdrawing compounds such as tetranitrofluorene and trinitrofluorene. However, although a sensitizing effect is observed, the effect is insufficient, or these additives may cause a decrease in chargeability, a decrease in potential stability during repeated use, and a decrease in sensitivity. , adverse effects such as an increase in residual potential were observed, and it was not suitable for practical use. Furthermore, the electron-withdrawing compound is toxic and cannot be put to practical use.

As can be seen from the above, electrophotographic photoreceptors are highly sensitive, especially to light with long wavelengths of 750 nm or more, have high potential stability during repeated use, and have little reduction in residual potential and sensitivity. Development was desired. "Objective of the Invention" The object of the present invention is to have high sensitivity, especially sufficient sensitivity to long-wavelength light such as semiconductor lasers, high potential stability, low residual potential, and durability during repeated use. The objective is to provide a high quality electrophotographic photoreceptor. “A Thousand Steps to Solving Problems” As a result of intensive research, we have developed the general formula (1) or the general formula (I
It has been discovered that a compound represented by I) or general formula (III) sensitizes a phthalocyanine pigment, and furthermore, the phthalocyanine pigment and a compound represented by general formula (1) or general formula (n) or general formula (III) are sensitized. It was discovered that the photoreceptor used has excellent potential stability and residual potential characteristics during repeated use compared to photoreceptors using other pigments,
We have arrived at the present invention. General formula (+) p friend Z General formula (H) ZZ General formula (I[I) Rt R! Z Z In general formula (I), general formula (■), and general formula (III), Z represents a sulfur atom or an oxygen atom. R' is an alwyl group, an alkoxy group, a monocyclic or two-ring fused 7-aryl group, a monocyclic or two-ring fused aryloxy group,
Or a heterocycle. Represents an l-valent group derived from force 1. In general formula (II), two R1's may be the same or different. R! and R1 each represent a hydrogen atom, an alkyl group, a monocyclic or bicyclic fused aryl group, or a monovalent group derived from a heterocycle, and may be the same or different. R4 represents a methylene group, a polymethylene group, a branched alkanediyl group, or an arylene group. Rl and R3, or R'' and R3 may be connected to each other. Also, the functional groups of Rt, R!, and Rs, and the divalent group of R4 may be unsubstituted or substituted. (1) In an electrophotographic photoconductor comprising a photoconductive layer provided on a conductive support, the photoconductive layer comprises a phthalocyanine pigment and the general formula (1), the general formula (If), or the general formula (II).
An electrophotographic photoreceptor for copying machines or optical printers, characterized in that it contains at least one of the compounds represented by [). (2) In an electrophotographic photoreceptor in which a single photoconductive layer is provided on a conductive support, the photoconductive layer contains a phthalocyanine pigment and the above general formula (1), general formula (n), or monocatalytic type (III). An electrophotographic photoreceptor for copying machines or optical printers, characterized in that it contains at least one of the compounds represented by: (3) In an electrophotographic photoreceptor provided with a leading iit1il having a laminated structure consisting of a charge generation layer and a charge transport layer on a conductive support, the charge generation HEN is combined with a phthalocyanine pigment and the general formula (I) or An electrophotographic photoreceptor for copying machines or optical printers, characterized in that it contains at least one kind of compound represented by general formula (n) or general formula (nl). (4) The electrophotographic photoreceptor for a copying machine or printer according to any of ( ]) to (3) above, wherein the light source of the copying machine or optical printer is a laser beam.

According to the present invention, it is possible to obtain an electrophotographic photoreceptor that is highly sensitive and highly durable and exhibits good characteristics in repeated use. (Specific structure and effects of the present invention) Phthalocyanine pigments used in the photoconductive layer of the electrophotographic photoreceptor of the present invention include those with different central metals, those with different crystal shapes, and those with a substituent on the benzene ring. Such,
A wide variety of phthalocyanine pigments can be used. For example, Special Publication No. 44-14106, Special Publication No. 45-810
No. 2, Special Publication No. 46-42511, Special Publication No. 46-425
No. 12, Japanese Patent Publication No. 49-4338, Japanese Patent Publication No. 18-1988
Metal-free phthalocyanine described in JP-A No. 2639, JP-A-62-47054, etc., JP-A-50-38543, JP-A-50-95852, JP-A-51-108847, JP-A-51-109841, etc. Copper phthalocyanine as described,
JP-A-59-49544, JP-A-59-166959
No., JP-A-62-275272, JP-A-62-286
No. 059, JP-A-62-67094, JP-A-63-3
No. 64, JP-A-63-365, JP-A-63-3716
No. 3, JP-A-63-57670, JP-A-63-802
No. 63, JP-A-63-116158, JP-A-63-1
Titanium phthalocyanine described in JP-A No. 98067, etc., JP-A-57-90058, JP-A-62-163060, JP-A-62-133462, JP-A-62-1770
No. 69, JP-A-63-73529, JP-A-63-43
Aluminum phthalocyanine described in No. 155 etc., JP-A-57146255, JP-A-57-147641,
Vanadyl phthalocyanine described in JP-A-57-148747, etc., JP-A-59-44053, JP-A-59-1
No. 28544, JP-A-59-133550, JP-A-5
9-133551, JP 59-174846, JP 59-174847, JP 60-59354.
No., JP-A-60260054, JP-A-60-2209
No. 58, JP-A-62-229254, JP-A-63-1
No. 7457, JP-A-59-155851, JP-A-63
Examples include halogenated metal phthalocyanines described in Japanese Patent Application Laid-open No. 27562, JP-A No. 63-56564, etc., but the present invention is not limited thereto, and various known phthalocyanines can be used. Typical core metals of phthalocyanine include metals such as copper, nickel, iron, vanadium, aluminum, gallium, indium, silicon, titanium, magnesium, cobalt, platinum, and germanium, as well as various metal-free phthalocyanines. It is being done. The crystal form was confirmed by X-ray crystal diffraction for each metal phthalocyanine and metal-free phthalocyanine.
For example, copper phthalocyanine has polymorphisms such as α-type, β-type, γ-type, δ-type, ε-type, η-type, ρ-type, etc., and metal-free phthalocyanine has polymorphisms such as α-type, β-type, χ-type, τ-type, etc. The polymorphism is
Titanyl phthalocyanine is known to have α-type, β-type, m-type, and other polymorphisms. Furthermore, substituted phthalocyanines in which the benzene ring of phthalocyanine is substituted with a halogen atom such as fluorine, chlorine, or bromine, an alkyl group, a carboxyl group, an amide group, a sulfonyl group, or other substituents are also known.

Furthermore, the phthalocyanine pigments used in the present invention include:
JP-A-63-233886, JP-A-63-18625
1, germanium naphthalocyanine described in JP-A-63-72761, etc., silicon naphthalocyanine described in JP-A-63-55556, JP-A-63-141070, etc., JP-A-63-186251, Kaisho 64-2
Tinnaphthalocyanine described in No. 061 etc., JP-A-63
Various metal naphthalocyanines described in No. 72761, JP-A No. 63-231355, and the like can also be mentioned. Each of these has a different absorption wavelength and is used as appropriate depending on the application, but when used in a laser beam printer etc. that uses a semiconductor laser as a light source, the absorption wavelength is 780 nm to 83 nm.
Phthalocyanine pigments having absorption at 0 nm are preferred.

Next, general formula (1) or general formula (I1) or one-ship method (
The compound represented by I[l] will be explained. Z represents a sulfur atom or an oxygen atom. General formula (I),
In the general formula (■) and the general formula (III), when any one of Rl to R3 is an alkyl group, examples of the alkyl group include a linear or branched alkyl group having 1 to 22 carbon atoms. In general formula (I), general formula (■), and general formula (III), when any one of R' to R3 is a substituted alkyl group, the substituent is a halogen atom (chlorine atom, bromine atom, fluorine atom), cyano 1 to 22 carbon atoms to which 1 to 3 groups, nitro group, phenyl group, or tolyl group are bonded
Examples include linear or branched substituted alkyl groups within the range of .

When R' is an alkoxy group or a substituted alkoxy group,
Examples thereof include the aforementioned alkyl groups or alkoxy groups having substituted alkyl groups or substituted alkoxy groups.

When any of R', R'', and R' is a monocyclic or two-ring fused aryl group, the aryl group is a phenyl group,
One example is the naphthyl group. Rl, Rg, R3
If any of them is a substituted monocyclic or substituted two-ring fused aryl group, the substituent is a halogen atom (chlorine atom, bromine atom, fluorine atom), a cyano group, a nitro group, a carbon atom number 1
Straight-chain or branched alkyl groups ranging from 1 to 5 carbon atoms; straight-chain or branched alkoxy groups containing 1 to 5 carbon atoms; straight-chain or branched alkyl groups containing 1 to 5 carbon atoms; and a phenyl group or naphthyl group having 1 to 3 acyl groups having a linear or branched alkyl group having 1 to 5 carbon atoms. When R1 is a substituted or unsubstituted monocyclic or two-ring fused aryloxy group, examples thereof include the above-mentioned aryloxy group having a substituted or unsubstituted monocyclic or two-ring fused aryl group. Can be done. Rl, R! , R3 is a monovalent group derived from a monocyclic or bicyclic fused heterocyclic ring, a pyrrolidinyl group, a piperidinyl group, a biperidino group, a morpholinyl group,
Examples include morpholino group, pyrrolyl group, imidazolyl group, biridyl group, pyrimidinyl group, indolinyl group, isoindolinyl group, indolyl group, isoindolyl group, penzimidazolyl group, quinolyl group, and isoquinolyl group. When Rl, Rt, R3 is a monovalent group derived from a monocyclic or two-ring fused heterocycle having a substituent, the substituent is a halogen atom (chlorine atom, bromine atom, fluorine atom), a cyano group, a nitro group. a phenyl group, tolyl group, benzyl group, phenethyl group, the aforementioned monocyclic or bicyclic fused type substituted with 1 to 3 linear or branched alkyl groups having 1 to 5 carbon atoms; 1 derived from heterocycle
The valence groups can be listed. When R1 and Rz1 or R3 and R' are connected, examples thereof include a trimethylene group, a tetramethylene group, a pentamethylene group, an oxydiethylene group (CH!
CHx O CHt CL ), and 1 to 3 hydrogen atoms of these divalent groups are halogen atoms (chlorine atom, bromine atom, fluorine atom), cyano group, nitro group, phenyl group, tolyl group, benzyl group , a phenethyl group, and a divalent group substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. Furthermore, the constituent parts of these divalent groups may be part of an aryl ring or a heterocycle. Rl, R1, R! is an alkyl group, an aryl group, or a l-valent group derived from a heterocycle having two or three substituents, and when R' is an alkoxy group or an aryloxy group, the substituents can take any combination. be able to. When R4 is a polymethylene group, examples thereof include a polymethylene group having a carbon number of 2 to 22; and when R4 is a branched alkanediyl group, a polymethylene group having a carbon atom number of 3 to 22 may be mentioned; Branched alkanediyl groups each having one monovalent free valence on each carbon atom can be mentioned.When R4 is an arylene group, 0-
, m- or p-phenylene groups, or naphthylene groups having one monovalent free valence on each of the two carbon atoms at any position.

Next, specific examples of the compounds represented by the above general formulas (1) to (Iff) are shown below, but the present invention is not limited to these compounds. Exemplified Compound (1) Exemplified Compound (2) Exemplified Compound (3) Exemplified Compound (4) Exemplified Compound (5) Exemplified Compound (lO) Exemplified Compound (6) Exemplified Compound (l1) Exemplified Compound (7) Exemplified Compound (12) Exemplified Compound (8) Exemplified Compound (13) Exemplified Compound (9) Exemplified Compound (14) Exemplified Compound Exemplified Compound Exemplified Compound S Exemplified Compound Exemplified Compound S Exemplified Compound Exemplified Compound O Exemplified Compound S Exemplified Compound Exemplified Compound S Exemplified Compound S S Exemplary compound S S Exemplary compound (29) Exemplary compound (30) O Exemplary compound (31) Exemplary compound (32) Urea represented by general formula (1), general formula (II), or general formula (III) in the present invention , thiourea compounds are all prepared by Beilsteins Handbuch.
derOrganichen Chaste J No. 12
It can be easily synthesized by the method described on page 262 of Vol. Electrophotographic photoreceptors using phthalocyanine materials are known to exhibit an inducticon effect, which causes a delay in the decay of the surface potential immediately after light irradiation, and this is the cause of reduced sensitivity. The reason for this is not clear, but it is thought that there are carrier traps on the surface of the phthalocyanine particles, and carriers generated by light irradiation are captured by these carrier traps, so that no attenuation of the surface potential is observed during this period. It is being done. The compounds of the present invention are considered to be sensitizers that reduce this induction effect, shorten the time during which the surface potential does not decay (induction period), and improve sensitivity as a result.

The use of compounds represented by the general formula (1) to general formula ([[I) of the present invention for use in electrophotographic photoreceptors is described in JP-A-58-102239 and JP-A-58-102240. ．． However, these claims are inventions as sensitizers for further sensitizing dye-sensitized spine photoconductors, and do not relate to photoconductors that are not dye-sensitized like the present invention. No sensitizing effect is described. Furthermore, the above specification does not describe the use of a phthalocyanine pigment as a photoconductive pigment in the present invention. Additionally, in the same specification, there is a description of using zinc oxide, which is an inorganic photoconductive pigment, as a photoconductive pigment, but these are also dye-sensitized inorganic photoconductors such as zinc oxide. only known to be effective in cases where
It was completely unexpected that the present invention would have the effect of reducing the inductone effect peculiar to phthalocyanine pigments.

Also, JP-A-56-149462 and JP-A No. 57-29050
Although the electrophotographic photoreceptor exhibits good electrophotographic properties after a single use as described in the above issue, after repeated use several times,
This results in a significant decrease in charging potential, decrease in sensitivity, and increase in residual potential, making it impossible to use it as a photoconductor for copiers and optical printers that are used repeatedly. In addition, when various additives such as electron-withdrawing compounds such as tetranitrofluorane and tetracyanoethylene are added for the purpose of increasing the sensitivity of phthalocyanine, the charging potential decreases and residues occur during repeated use. causes an increase in electrical potential.

However, the compound represented by the general formula (■), general formula (n), or general formula (III) of the present invention does not cause deterioration of the above-mentioned repeatability characteristics and sensitizes phthalocyanine, resulting in high sensitivity and good performance. Suitable for use in copying machines and optical printers that require high repeatability. The electrophotographic photoreceptor of the present invention comprises the above-described phthalocyanine pigment and general formula (1), general formula (■), or general formula (III).
It has a photoconductive layer containing a compound represented by. Various forms of electrophotographic photoreceptors are known, and the electrophotographic photoreceptor of the present invention may be any of these types. Generally, the electrophotographic photoreceptor of the present invention is used with the layer structure illustrated below. (1) A phthalocyanine pigment and the general formula (1) or the general formula (II) or the general formula (I
A single photoconductive layer containing the compound II). (2) Phthalocyanine pigment and general formula (
1) or a charge generating layer containing a compound represented by the general formula (II) or the general formula (I[l), and a charge transporting medium layer provided thereon.

(3) A charge transport medium layer is provided on a conductive support, and a phthalocyanine pigment and a general formula (1) or a general formula (■) are provided on the charge transport medium layer.
Or one provided with a charge generation layer containing a compound represented by general formula (III). To prepare an electrophotographic photoreceptor of type (1), a phthalocyanine pigment is dispersed in a solution in which a compound represented by general formula (1), general formula (II), or general formula (III) and a binder are dissolved. ,
This can be applied onto a conductive support and dried. Alternatively, a phthalocyanine pigment is dispersed in a binder solution, and then added to this solution with general formula (2H) or general formula (n) or general formula (
A coating liquid may be prepared by dissolving the compound represented by II). In the case of an electrophotographic photoreceptor of type (υ), a charge transport agent, which will be described later, can be included in the photoconductive layer for the purpose of assisting charge transfer, and electrophotographic photoreceptors with this composition are common. The thickness of the photoconductive layer is preferably 3 to 50 μm, preferably 5 to 30 μm. To prepare an electrophotographic photoreceptor of type (2), first, phthalocyanine and general formula (1) or A charge generating layer is provided by dispersing the compound represented by the general formula (■) or the general formula (I[I) in a suitable solvent or, if necessary, a solvent in which a binder has been dissolved, and drying it.Alternatively, a phthalocyanine A coating solution may also be prepared by dispersing the pigment in a solvent or a solvent in which a binder is dissolved, and then melting the compound represented by the general formula (+) or the general formula (ff) or the general formula (v1). Good. After that, a solution containing a charge transport compound and a binder is applied thereon and dried to form a charge transport layer.The thickness of the charge generation layer at this time is 4μ or less, particularly 0.1~
2 μ is preferable, and the thickness of the charge transport layer is 3 to 50,1/,
Particularly preferred is 5 to 30μ. Further, the charge generation layer of the present invention includes a thin film containing a compound represented by formula 1a (1), general formula (■), or general formula (I [I)] between the charge generation layer and the conductive support. A charge generating layer of a phthalocyanine pigment is provided on the layer by vapor deposition, and by diffusion of the upper layer coating solvent, the phthalocyanine pigment and the phthalocyanine pigment represented by the general formula (]) or the general formula (]l) or the general formula (1) are formed. Alternatively, a phthalocyanine pigment is vapor-deposited onto a conductive support, and a compound of general formula (1) or general formula (It
) or by applying a solution containing the compound represented by general formula (III) and allowing it to coexist with a phthalocyanine pigment. Phthalocyanine # deposited in this case! The thickness of the material is 0.001μ~lp, especially 0.001μ~lp.
01μ to 0.5 is preferable. Type (3) electrophotographic photoreceptor is produced by reversing the stacking order of the charge generation layer and charge transport layer of type (2). The photoreceptor of type (1) in the present invention has relatively good repeating characteristics because the phthalocyanine itself has a charge transfer ability compared to azo dye, etc., but the photoreceptor of type (2)
(Compared to the three types of photoreceptors, it has low sensitivity, and the decrease in charging potential and increase in residual potential due to repeated use are also somewhat large. Therefore, type (2) is the usage form of the present invention.
and (3) are preferred; in this form, an electrophotographic photoreceptor with extremely high sensitivity, little change in charging potential after repeated use, low residual potential, high rigidity, and high durability can be obtained. (]) The phthalocyanine material used in the photoreceptors of types (2) and (3) is pulverized and dispersed using a known dispersion machine, such as a ball mill, sand mill, or vibration mill. Hereinafter, preferably << is 0.1
It is used after being crushed to ~2I. If the amount of phthalocyanine pigment used in the electrophotographic photoreceptor of type (1) is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor, the strength of the electrophotographic photosensitive layer will be weakened, and the electrophotographic photoreceptor will have poor sensitivity. The proportion of the phthalocyanine pigment in the layer is 0.01 to 2 times the weight of the binder, preferably 0.05 to 1
Double the weight is better. When a charge transport compound is used in combination, the proportion of the charge transport compound is 0.1 to 2 times the weight of the binder, preferably 0.
．． A range of 3 to 1.3 magnification is good. Further, the content of the compound represented by general formula (1), general formula (II), or general formula (III) is 0.01 to 1% relative to the phthalocyanine pigment.
Heavy-duty magnification, preferably 0.02-0. A range of 4 times the weight is appropriate. In addition, when coating and forming a disazo compound-containing layer that becomes a charge coloring layer in type (2) and (3) electrophotographic photoreceptors, the amount of phthalocyanine pigment used is preferably 0.1 to 50 times the weight of the binder resin. If this is the case, sufficient photosensitivity cannot be obtained.The ratio of the charge transport compound in the charge transport medium to the binder is 0.01.
~10 times by weight, preferably 0.2 to 2 times by weight. In this case as well, the content of the compound represented by general formula (1), general formula (■), or general formula (I[[) is 0.01 to 1 times by weight, preferably 0.02 to A range of 0.4 times the weight is appropriate.

In addition, in types (2) and (3) of the photic bodies, JP-A-6
0-196767, JP-A-60-254045, and JP-A-60-262159, charge transport compounds such as hydrazone compounds and oxime compounds are added to the charge generation layer. You can also do it.

As the charge transport material used in combination with the type (1) photosensitive layer used in the present invention, a wide variety of known charge transport materials can be mentioned. Charge transport materials can be classified into two types: compounds that transport electrons and compounds that transport holes. Compounds that transport electrons include compounds having an electron-withdrawing group, such as 2,4.7-}linitro-9-fluorenone, 2,4,5.7-tetranitro-9-fluorenone, 9-dicyanomethylene-2. 4.7-Trinitrofluorenone, 9-dicyanomethylene-2.4.5.7-tetranitrofluorenozo, tetranitrocarbazole chloranil, 2.3-dichloro-5,6-dicyanobenzoquinone, 2,4.7 Examples include -trinitro9.10-phenanthrenequinone, tetracyanophthalic anhydride, tetracyanoethylene, and tetracyanoquinone dimethane. Compounds that transport holes include compounds that have an electron donating group. For example, in the case of polymers, (1) Special Publication No. 34-1
Bilibinylcarbazole and its derivatives described in Publication No. 0966.

．． (2) Special Publication No. 18674, Special Publication No. 18674, Special Publication No. 18674, Special Publication No. 18674
Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-(4'-dimethylaminophenyl)-5-phenyloxazole, poly-
Vinyl polymers such as 3-vinyl-N-ethylcarbazole. (3) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 43-19193. (4) Special Public Service 1984-
Condensation resins such as birene-formaldehyde resin, propylene-formaldehyde resin, and ethyl rubazole-formaldehyde resin described in Japanese Patent No. 13940 and the like.
(5) JP-A-56-90883 and JP-A-56-16
Among the various triphenylmethane polymers and low-molecular polymers described in No. 1550, (6) triazole derivatives described in U.S. Pat. No. 3,112,197 and the like. (7) U.S. Patent No. 3
, 189,447, etc. (8) Imidazole derivatives described in Japanese Patent Publication No. 37-16096 and the like. (9) U.S. Patent No. 3,615.402, U.S. Patent No. 3,82
No. 0,989, No. 3,542.544, Special Publication No. 1977-
No. 555, JP 51-10983, JP 51-9
No. 3224, JP-A-55-10866'r, JP-A-Sho 5
5-156953, JP-A-56-36656, publications, etc., polyarylalkane derivatives. 0ω
U.S. Patent No. 3,180,729, U.S. Patent No. 4,2
No. 78,746, JP-A-55-88064, JP-A-5
5-88065, JP 49-105537, JP 55-51086, JP 5 6-8 0 0 5
No. 1, JP-A-56-88141, JP-A-57-45
No. 545, JP-A-54-112637, JP-A-55-
．． Vilazoline derivatives and virazolone derivatives described in Patent No. 74546, publications, etc. 00 U.S. Patent No. 3,615,404, Japanese Patent Publication No. 51-10105, Japanese Patent Application Publication No. 54-83435, Japanese Patent Application Publication No. 54-11083
No. 6, JP-A-54-119925, JP-A-46-37
Phenylenediamine derivatives described in No. 12, Japanese Patent Publication No. 47-28336, gazettes, etc. 07J
U.S. Patent No. 3,567,450, Japanese Patent Publication No. 49-357
No. 02, West German Patent (DAS) 1 110518, U.S. Patent No. 3,180.703, U.S. Patent No. 3,240
, 597, U.S. Patent No. 3,658,520, U.S. Patent No. 4,232,103, U.S. Patent No. 4,175,9
No. 61, U.S. Patent No. 4,012,376, Japanese Unexamined Patent Application No. 1983
-144250, JP-A-56-119132, JP-B-39-27577, JP-A-56-22437 specification, gazettes, and the like. Side Amine-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501. 04 N,N-bicalbasil derivatives described in US Pat. No. 3,542,546 and the like. OS Oxazole derivatives described in US Pat. No. 3,257,203 and the like. 0[9 Styryl anthracene derivatives described in JP-A-56-46234 and the like.

Fluorenone derivatives described in JP-A-54-110837 and the like. 08) U.S. Patent No. 3,717,462, Japanese Unexamined Patent Publication No. 1983-
No. 59143 (corresponding to U.S. Patent No. 4,150,987), JP-A-55-52063, JP-A-55-5206
No. 4, JP-A-55-4676 "No. 0, JP-A-55-85
No. 495, JP-A-57-11350, JP-A-57-1
Hydrazone derivatives disclosed in No. 48749, JP-A-57-104144, etc. 0! D U.S. Patent No. 4,047,948, U.S. Patent No. 4.047,949, U.S. Patent No. 4,265,99
No. 0, U.S. Patent No. 4,273,846, U.S. Patent No. 4
, 299.8.97, U.S. Patent No. 4,306,008
Benzidine derivatives described in the specification etc. -el JP-A-58-190953, JP-A-59-
No. 95540, JP-A-59-97148, JP-A-59-Sho.
Examples include stilbene derivatives described in Japanese Patent No. 195658. In the present invention, the photoconductive substance is not limited to the compounds listed in (1) to I2Φ, and all conventional photoconductive substances can be used. It is also possible to use two or more types of these photoconductive substances in combination depending on the case.

The electroconductive support used in the electrophotographic photoreceptor of the present invention is an aluminum rim, a metal plate made of copper, zinc, stainless steel, etc., a metal drum, or a sheet made of plastic, yam, etc., or a cylindrical substrate with aluminum, Indium oxide, SnO. , paper coated with a conductive material such as carbon by vapor deposition or dispersion coating, or coated with a conductive polymer, or treated with conductive treatment using inorganic salts such as sodium chloride, calcium chloride, or organic quaternary ammonium salts; Uses phenolic resin drums and Bakelite drums molded with carbon. It will be done. The resin used in the charge generation layer of type (2) and type (3) of the present invention can be selected from a wide range of insulating resins, such as polyester resin, cellulose resin, acrylic resin, polyamide resin, polyvinyl butyral resin, Phenoxy resin, polyvinyl formal resin, polycarbonate resin, styrene resin, polybutadiene resin,
Examples include polyurethane resin, epoxy resin, silicone resin, vinyl chloride resin, vinyl chloride-vinyl acetate resin, etc., but are not limited thereto. As the resin used for the charge transport layer, it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. As such a high molecular weight polymer,
For example, the following can be mentioned, but of course it is not limited to these. Polycarbonate, polyester, methacrylic IBFa
, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-ptadiene copolymer, vinyl chloride↓lidene-acrylic nitrile copolymer, vinyl chloride-hinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride Copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, polyN-
Examples include vinyl carbazole.

The binder for the photoconductive layer of type (1) can be appropriately selected from the binders for the charge generation layer and charge transport layer described above.

These binders can be used alone or as a mixture of two or more. When producing the electrophotographic photoreceptor of the present invention, additives such as a plasticizer or a sensitizer may be used together with the binder. Plasticizers include biphenyl, biphenyl chloride, 0-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid, methylnaphthalene, penzophenone, chlorinated paraffin, . Polypropylene, boristyrene, dilaurylthiodipionate, 3.5-dinitrosalicylic acid, dimethyl phthalate, dibutyl phthalate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, various fluorohydrocarbons Examples include the following. In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor.

Examples of chloraniol include chloranil, tetracyanoethylene,
Methyl violet, rhodamine B, cyanine dye, merocyanine dye, pyrylium dye, thiavirylium dye, compounds described in JP-A-58-65439, JP-A-58-102239, JP-A-58-129439, JP-A-62-71965, etc. I can list the following. Coating liquids include alcohols (e.g. methanol, ethanol, isobrobanol, etc.), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, silohexanone, etc.), amides (e.g. N, N-
dimethylformamide, N,N-dimethylacetamide, etc.), esters (e.g., methyl acetate, ethyl acetate,
butyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane, monoglyme, diglyme, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, methylchloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene, etc.) These can be used alone or in combination. Application can be carried out using general-purpose coating methods such as spraying, roller coating, sinter coating, blade coating, and dip coating. Furthermore, in the present invention, an adhesive layer or barrier layer can be provided between the conductive support and the photoconductive calendar, if necessary. Materials used for these layers include, in addition to the high molecular weight polymer used for the binder, gelatin, casein, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and JP-A-5-9-8-4.
2 4 'l. These include vinylidene chloride-based polymer latex, polymer latex described in JP-A-59-114544, aluminum oxide, etc., and the thickness of these layers is 0.1 to 5.
μm is preferred.

Further, in the present invention, an overcoat layer can be provided on the photoconductive layer if necessary. This overcoat layer may be mechanically matted or a resin layer containing a matting agent. In this case, matting agents include particles of polymers such as silicon dioxide, glass particles, alumina, starch, titanium oxide, zinc oxide, polymethyl methacrylate, polystyrene, and phenolic resin;
and U.S. Patent Nos. 2,701,245 and 2,99.
This includes the matte described in the specification of No. 2,101. Two or more of these can be used in combination. The resin used for the overcoat layer can be selected from various known resins in addition to those used for the photoconductive layer. The present invention has been described in detail above, and the electrophotographic photoreceptor of the present invention has excellent irradiation resistance, little change in charging potential during repeated use, and low residual potential, high printing durability, and high durability. It is. The electrophotographic photoreceptor of the present invention,
It can be widely applied to fields such as electrophotographic copying machines, as well as lasers and photoreceptors for printers that use cathode ray tubes as light sources.

In particular, since the intensity is high even in the long wavelength range, the present invention will be specifically explained using examples using semiconductor lasers, He-Ne lasers, etc. as light sources. It's not a thing. In the examples, "parts" indicate "parts by weight."

Example 1 ε type steel phthalocyanine (Liophoton EPPC: manufactured by Toyo Ink ■) 3.0 parts Exemplary compound (3) 0.3 parts Polyester resin (Vylon 200: manufactured by Toyobo ■) 3.0 parts Hydrazine compound Tetrahydrofuran 100 parts to 500 parts
The mixture was placed in a glass container with glass beads and dispersed for 60 minutes using a paint shaker (Toyo Seiki Seisakusho ■).The glass beads were then filtered out to obtain a photoconductive layer dispersion. Next, this photoconductive layer dispersion was applied onto a conductive support (a 75 μm polyethylene terephthalate film with a vapor-deposited aluminum film on the surface, surface resistance 103Ω) using a wire urand rod. Dry for 2Q
An electrophotographic photoreceptor having a photoconductive layer of II m was obtained.

Next, the electrical properties of the produced electrophotographic photoreceptor were determined using EPA-8
100 (manufactured by Kawaguchi Electric ■), corona charging at +8, OkV using the scutch method, and monochromatic light of 780 nm
Measurement was performed under conditions of exposure with a light intensity of mW/n{.
The surface potential immediately after charging (Vo), the ratio of the surface potential 10 seconds after charging to ■0 is the charge retention rate (DD,,)
, and as sensitivity, the surface potential before exposure is attenuated by light to 1/
The exposure amount that becomes 2 (E,.) and the exposure amount that becomes 1/10 (E,.)
．． ．． ), the exposure amount as residual potential (Vl) is 100μJ/
When the surface potential at the time of cm'' was investigated, it was found that V o +6 5 5 V Eso 2.4 p J/c+++2E96
8. 9 pJ/cm”onto
74%V. It was +23V. Comparative Example 1 An electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that Exemplary Compound (1) was removed from the photoconductive layer coating solution of Example 1. Example 1 Electrical characteristics of this electrophotographic photoreceptor
When measured under the same conditions as Vo +670V Es++ 3. 8 B J /cm”E,.

It was 12.6μJ/Cl blade DD+e 75% Vm +22V. Example 2 3 parts of ε-1 copper phthalocyanine (Liophoton EPPC), 0.3 parts of exemplified compound (3) and polyester resin (
After dispersing 3 parts of Byron 200) in 100 parts of tetrahydrofuran in a ball mill for 20 hours, a conductive support (as described above) was dispersed using a wire round rod.
A charge generation layer having a thickness of 0.5 .mu.m was obtained by coating and drying the mixture on the evaporated film 1).

Next, a solution of hydrazine compound C11 and 10 parts of bisphenol 8 polycarbonate dissolved in 50 parts of dichloromethane was applied onto the charge generation layer using a wire round loft and dried to form a charge transport layer with a thickness of 20 μm. , an electrophotographic photoreceptor was created. The electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 1 except that it was corona charged at -8 kV. As a result, the DO. . 78% V. 24V. After that, the two steps of charging and exposure were repeated 10,000 times and the electronic characteristics were examined, but there was almost no change from the characteristics before the repetition. Comparative Example 2 Illustration of Example 2 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2, except for compound (3).The electrical properties of this electrophotographic photoreceptor were measured under the same conditions as in Example 2.Vo -738V Eso 2. Op J/Cll"Eve
5.8μJ/cm" OD1. 79% Vl.24V. Example 3
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2, except that X-type metal-free phthalocyanine (Fastogen Blue 8120, manufactured by Dainippon Ink ■) was used instead of PC). The electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 2. As a result, Vo -740V Eso O. 6μJ/cm" E,. 1.7μJ/c■2 00..77% ■Blade 12V. After that, the two steps of charging and exposure were repeated 10,000 times and the electrical characteristics were examined, but the characteristics before repetition were Comparative Example 3 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 3, except that the exemplified compound (3) of Example 3 was removed.

When the electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 2, Vo -740V BS@0. 9 p J /crs”E 啼O
2. 7μJ/cta″DD+
. 78%V. It was t5V. Example 4 ε-1 type copper phthalocyanine (Riophoto 7EP) of Example 2
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2, except that α-type titanyl copper phthalocyanine (manufactured by Toyo Ink ■) was used instead of PC). The electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 2. As a result, Vo -710V Eso O. 40 μJ/CI” Eqo 1, 2 (tJ/aafiDD.
It was 74% V* 13V. After that, the two steps of charging and exposure were repeated 10,000 times and the electrical properties were examined, but there was almost no change from the properties before repeating. Comparative Example 4 The electrical properties of an electrophotographic photoreceptor were measured under the same conditions as in Example 2 in exactly the same manner as in Example 3 except for the exemplified compound (3) of Example 4. As a result, Vo -720V E. 0.5 μJ/c 2 E drop 0 1.5 μJ/cm” DD+. 77% V* IIV. Examples 5 to 12 The exemplified compound in Table 1 was used instead of the exemplified compound (3) in Example 2. An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2 except that the electrophotographic photoreceptor was used.
It is shown in The electrical characteristics were measured under the same conditions as in Example 2. Example 11 X-type metal-free phthalocyanine (manufactured by Dainippon Ink ■, Fas
togen Blue 8] 20) was milled in a ball mill for 20 hours with a solution of 3 parts of polyester resin (Vylon) dissolved in 100 parts of chlorobenzene, and then 0.3 parts of Exemplified Compound (3) was dissolved. The mixture was coated onto a conductive support using a wire rough rod and dried to obtain a charge generation layer having a thickness of 0.5 μm. Thereafter, a charge transport layer was provided by the same method as in Example 2 to produce an electrophotographic photoreceptor. The electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 2. As a result, Vo -735V Eqo O. 6 pJ/cm”E,.

1. 7μJ/crs”DD+o 7
It was 7% VIIIV. After that, the two steps of charging and exposure are done to, oooi.
I repeatedly checked the electrical characteristics, but there was almost no change from the characteristics before the repetition. Example 1 and Comparative Example 1, Example 2, 5 to 10 and Comparative Example 2,
Example 3, l1 and Comparative Example 3, and Example 4 and Comparative Example 4
When compared, the electrophotographic photoconductor to which the compound represented by the general formula (+) was added was 1.
．． 5 to 2 times more sensitive, but chargeable, dark decay,
It can be seen that there is no large difference in residual potential and that a good electrophotographic photoreceptor is maintained. Furthermore, Examples 2, 3, 4, 13
It was confirmed that the electrical characteristics after repeated use to and ooo times were almost unchanged from the initial characteristics.

As described above, the electrophotographic photoreceptor shown in the examples satisfies the purpose of the present invention, which is "a highly durable electrophotographic photoreceptor with high sensitivity, high potential stability during repeated use, and low residual potential." It can be seen that it is.

Claims (4)

[Claims] (1) In an electrophotographic photoreceptor in which a photoconductive layer is provided on a conductive support, the photoconductive layer contains a phthalocyanine pigment and a compound represented by the following general formula (I), general formula (II), or general formula (III). An electrophotographic photoreceptor for copying machines or optical printers, characterized in that it contains at least one of the following. General formula (I) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula (I) , general formula (II), and general formula (III), Z represents a sulfur atom or an oxygen atom. R^1 represents an alkyl group, an alkoxy group, a monocyclic or bicyclic fused aryl group, a monocyclic or bicyclic fused aryloxy group, or a monovalent group derived from a heterocycle. In general formula (III), two R^1's may be the same or different. R^2 and R^3 are each a hydrogen atom, an alkyl group,
It represents a monocyclic or two-ring fused aryl group, or a monovalent group derived from a heterocycle, and may be the same or different from each other. R^4 represents a methylene group, a polymethylene group, a branched alkanediyl group, or an arylene group. R^1 and R^2 or R^2 and R^3 may each be connected. (2) The photoconductive layer contains a phthalocyanine pigment and the general formula (
The electrophotographic photoreceptor for copying machines or optical printers according to claim (1), which is a single layer containing a compound represented by I) or general formula (II) or general formula (III). (3) The photoconductive layer contains a phthalocyanine pigment and the general formula (
Electrophotography for copying machines and optical printers according to claim (1), comprising a charge generation layer and a charge transport layer containing a compound represented by I) or general formula (II) or general formula (III). Photoreceptor. (4) The electrophotographic photoreceptor for a copying machine or optical printer according to any one of claims (1) to (3), wherein the light source of the copying machine or optical printer is a laser beam.