JPH031156A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the electrophotographic sensitive body which has a high sensitivity and has high potential stability even after repetitive use by incorporating a phthalocyanine pigment and >=2 kinds of respectively specific compds. into a photoconductive layer. CONSTITUTION:The phthalocyanine pigment, at least one kind of the compds. expressed by formulas I,II, etc., and at least one kind of the compds. expressed by formula III are incorporated into the photoconductive layer. In the formulas I to III, Z denotes a sulfur atom, oxygen atom; R<1> to R<6> denote a hydrogen atom, alkyl group, etc.; R<7> denotes a bivalent arylene group; aralkylene group, etc.; R<12>, R<13> denote an alkyl group, aryl group, etc.; R<14> denotes a hydrogen atom, aryl group, etc.; R<15> denotes an alkyl group, phenyl group; X<1> denotes -0-, methylene group, etc.; X<2> denotes benzene, the atom group necessary for forming a naphthalene ring; Ar<2> denotes a monovalent arom. hydrocarbon group, heterocyclic group. The electrophotographic sensitive body having the high sensitivity and the high potential stability after the repetitive use is obtd. in this way.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to an electrophotographic photoreceptor comprising a photoconductive layer comprising a charge generating material, a charge transporting material, and a sensitizer on a conductive support. It is.

"Prior Art" Electrophotographic photoreceptors that are sensitive to visible light have been developed for application to copying machines, optical printers, and the like. Conventionally, such electrophotographic photoreceptors include selenium, zinc oxide,
Photoreceptors based on inorganic photoconductive materials such as cadmium sulfide have been widely used. However, such inorganic photoreceptors do not necessarily satisfy the performance required for electrophotographic photoreceptors such as copying machines, such as photosensitivity, thermal stability, moisture resistance, and durability.

For example, a selenium photoreceptor crystallizes due to heat or fingerprint stains when touched, so the above-mentioned characteristics required for an electrophotographic photoreceptor tend to deteriorate.

Further, electrophotographic photoreceptors using cadmium sulfide 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.
Electrophotographic photoreceptor consisting of N-vinylcarbazole and 2.4.7-)dinitrofluoren-9-one (US Pat. No. 3,484°237), poly-N-vinylcarbazole sensitized with biryllium base dye Things (Tokuko Showa 48-
25Ei58), an electrophotographic photoreceptor containing an organic pigment as a main component (Japanese Patent Application Laid-Open No. 4'1-37543), an electrophotographic photoreceptor containing a eutectic complex consisting of a dye and a resin as a main component (Japanese Patent Application Laid-Open No. 47-1988) -10785).

However, although these photoreceptors have improved the drawbacks of the inorganic photoreceptors to some extent, they generally have low photosensitivity and cannot be used repeatedly, so they do not fully meet the requirements as 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 such as sensitivity and durability of the electrophotographic photoreceptor, and it has the advantage that materials suitable for forming the coating film of the electrophotographic photoreceptor can be selected from a wide range.

Various organic dyes and organic pigments have been developed as effective organic charge generating substances used in the charge generating layer of such functionally separated electrophotographic photoreceptors, such as azo pigments of various structures, perylene pigments, etc. , polycyclic quinone pigments, square methine dyes, etc. are used.

However, although these pigments show relatively good sensitivity in the short or medium wavelength range, their sensitivity in the long wavelength range is low, making them difficult to use in laser printers that use semiconductor laser light sources that are expected to have high reliability. was difficult.

``Till!J, which the invention seeks to solve.Currently, the oscillation wavelength of gallium-aluminum-arsenide light-emitting devices, which are widely used as semiconductor lasers, is 750 nm or more.Electrons that are highly sensitive to such long wavelength light In order to obtain a photographic photoreceptor, many studies have been made in the past. For example, a method of adding a new window increasing agent for longer wavelengths to a photosensitive material such as 3e, CdS, etc., which has high sensitivity in the visible light region. However, as mentioned above, Se and CdS depend on temperature,
Environmental resistance against humidity, etc. is insufficient.

Furthermore, as mentioned above, the sensitivity of many known organic photoconductive materials is usually limited to the visible light region of 70 Q nm or less, and there are few materials that have sufficient sensitivity in longer wavelength regions.

Among these, phthalocyanine compounds, which are one of the organic photoconductive materials, are known to have a sensitivity range expanded to longer wavelengths compared to the pigments and dyes mentioned above. There are deficiencies in electrophotographic properties such as gender. 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, 8-type copper phthalocyanine,
I-type metal-free phthalocyanine and m-type titanyl phthalocyanine are known. These phthalocyanines have sensitivity in the long wavelength range, but the sensitivity is insufficient for use in copiers or optical printers, and furthermore, in repeated use,
It had drawbacks such as insufficient potential stability and large residual potential, and 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 has been 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 none were suitable for practical use. Furthermore, the electron-withdrawing compound is toxic and cannot be put to practical use.

By the way, in general, in electrophotographic photoreceptors, a charge transport material that is effective for a certain charge generating substance is not necessarily effective for other charge generating substances; It cannot be said that a charge generating substance that is effective for charge transporting substances is also effective for other charge transporting substances.

In this way, an appropriate combination of charge-generating substances and charge-transporting substances is required, and regarding this combination,
Although some regularity can be seen, it does not apply to all substances.

for example,! It has been proposed to use ionization potential as a guideline for selecting MN transport materials to be combined with transport-generating materials, but these results are based on specific similar materials;
Lacking film properties, it has not been possible to clearly explain the electrophotographic characteristics between different materials.

As described above, the current situation is that various combinations of charge-generating substances and charge-transporting substances have been studied through trial and error.

As you can see from the above, high sensitivity, especially at 750 nm.
It has been desired to develop an electrophotographic photoreceptor that is highly sensitive to light with the above long wavelengths, has high potential stability during repeated use, and exhibits little reduction in residual potential and sensitivity.

``Object 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, and to have high potential stability (low residual potential, low durability, etc.) during repeated use. The object of the present invention is to provide an electrophotographic photoreceptor with high quality.

"Means for Solving the Problem" As a result of intensive research, we have discovered that the compounds represented by -a formulas (1) to (VI) sensitize phthalocyanine pigments, and furthermore, we have discovered that compounds represented by formulas (1) to (VI) sensitize phthalocyanine pigments and -form CI )～(
A photoreceptor using a compound represented by Vl) and a compound represented by -formation (■) has superior potential stability and residual potential characteristics during repeated use compared to photoreceptors using other pigments. They discovered this and arrived at the present invention.

-Formation (+) General formula (III) General formula <rv> General formula (V) General formula (■) General formula (Vl) In general formulas (1) to (■), Z represents a sulfur atom or an oxygen atom. represent.

R1, R1, Rs, Ra, Rs, and R& each represent a monovalent group derived from a hydrogen atom, an alkyl group, or a heterocycle, and may be the same or different from each other.
, or R1 and R4 may each be connected. −
In formation (1), RIRl, R'J, and R4 may be linked together to form a bridged ring as a whole. R? represents a divalent arylene group, an aralkylene group, a polymethylene group or an alkyl group.

In - formation (V), R1 represents an alkyl group, an alkoxy group, a monocyclic or bicyclic aryl group, a monocyclic or bicyclic aryloxy group, or a monovalent group derived from a heterocycle; The two R''s may be the same or different.

R9 and RIo represent an alkyl group, an aryl group, or an aralkyl group, and R9 and RIo may be the same or different groups.

RI 1 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Furthermore, Ar and R11 may form a ring.

R1! , R13 is an alkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an amino group, and a hydrogen atom,
Represents a halogen atom.

These may be the same or different.

R14 represents a hydrogen atom, an alkyl group, or an aryl group.

R15 represents an alkyl group or an aryl group.

\/ \/ \/ \/ XI is N , 0, S,, Se or substituted with H1
+ also represents a methylene group.

Xz represents an atomic group necessary to form a benzene or naphthalene ring.

n represents an integer of 0 or 1.

ArI and Arz represent a monovalent aromatic hydrocarbon group or a monovalent heterocyclic group.

That is, the present invention provides (1) an electrophotographic photoreceptor in which a photoconductive layer is provided on a conductive support, in which the photoconductive layer contains a) a phthalocyanine pigment; b)
- for a copying machine or for an optical printer, characterized in that it contains at least one of the compounds represented by formulas (1) to (Vl), and c) - also one of the compounds represented by the R9 formula (■) Electrophotographic photoreceptor for printers.

(2) The electrophotographic photoreceptor for copying machines or printers according to (1) 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 a highly durable electrophotographic photoreceptor that has high sensitivity 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,
Various phthalocyanine pigments can be used 6 For example, Japanese Patent Publication No. 44-14106, Japanese Patent Publication No. 45-8102
, Special Publication No. 46-42511, Special Publication No. 46-42512,
Metal-free phthalocyanine described in JP-A-49-4338, JP-A-58-182639, JP-A-62-47054, etc., JP-A-50-38543, JP-A-50-95852,
JP 51-108847, JP 51-109841
Copper phthalocyanine described in JP-A-59-49544, etc.
JP-A-59-166959, JP-A-62-275272
, JP-A-62-286059, JP-A-62-67094
, JP-A-63-364, JP-A-63-365, JP-A-6
3-37163, JP-A-63-57670, JP-A-63
-80253, JP-A-63-116158, JP-A-63
-198067 etc., JP-A-57-90058, JP-A-62-163060. JP-A-62-133462, JP-A-62-177069.
, JP-A-63-73529, JP-A-63-43155, etc., aluminum phthalocyanine, JP-A-57-1
46255, JP-A-57-147641, JP-A-57-
Vanadyl phthalocyanine described in JP 59-44053, JP 59-128544, JP 59-133550, JP 59-133551, JP 59-174846, JP 59-174847, etc.
JP-A-60-59354, JP-A-60-560054,
JP-A-60-220958, JP-A-62-229254
, JP-A-6317457, JP-A-59-155851,
Examples include halogenated metal phthalocyanines described in JP-A-63-27'562 and JP-A-63-56564, but the invention is not limited thereto, and various known phthalocyanines can be used.

Typical core metals of phthalocyanines include metals such as nickel, iron, vanadium, aluminum, gallium, indium, silicon, titanium, magnesium, cobalt, platinum, and germanium, as well as metal-free phthalocyanines. Are known.

The crystal form was confirmed by X-ray crystal diffraction for each metal phthalocyanine and metal-free phthalocyanine.
For example, in copper phthalocyanine, α type, β type, τ type, δ type
For metal-free phthalocyanine, there are α-type, β-type, χ-type, τ-type and other polymorphisms; for titanyl phthalocyanine, there are α-type, β-type, m-type, etc. types and other polymorphisms are known. 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
Germanium naphthalocyanine described in JP-A-63-55556, JP-A-63-141070, etc., JP-A-63-186251, JP-A-63-186251, JP-A-63-141070, etc. 1986-20
Tin naphthalocyanine described in No. 51 etc., JP-A-63-
Various metal naphthalocyanines described in JP-A-63-231355 and the like can also be mentioned.

Each of these 6 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, it is 780 nm ~
Phthalocyanine pigments having an absorption at 830 nm are preferred.

Next, a compound represented by the general formula (Vl) that improves the photoconductivity of a photoconductive layer using a phthalocyanine pigment will be explained.

In general formulas (1) to (Vl), Z represents a sulfur atom or an oxygen atom.

When any of R1, R'', R', R', R'%R' is an alkyl group, the alkyl group is a linear or branched alkyl group having 1 to 22 carbon atoms or a substituted alkyl group. The basics are given.

Examples of substituents bonded to an alkyl group include halogen atoms (chlorine atom, bromine atom, fluorine atom), cyano group, nitro group, phenyl group, tolyl group, and trifluoromethyl group, and the number of substituents is 1. It is from 1 to 3 pieces.

R', R", R", R', R', R" (7
) is an aryl group, examples of the aryl group include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, and a substituted or unsubstituted anthranyl group. Substituents include halogen atoms (chlorine atoms, bromine atoms,
fluorine atom), cyano group, nitro group, trifluoromethyl group, linear or branched alkyl group having 1 to 5 carbon atoms, carboxyl group, alkoxycarbonyl group, cyano group, nitro group or halogen atom ( chlorine atom,
Straight chain with 1 to 5 carbon atoms substituted with 1 to 3 bromine atoms, fluorine atoms (in the case of 2 or 3 monosubstitutions, they may be the same or different from each other) or a branched alkyl group, a linear or branched alkoxy group having 1 to 5 carbon atoms, the number of substituents is 1 to 3, and the number of substituents is 2 or 3. They may be the same or different from each other.

R', R'', R3, R', R3, R'' 0) When 11TE is derived from a heterocycle, a monosubstituted or unsubstituted pyrrolidinyl group, piperidinyl group, piperidino group, morpholinyl group, morpholino group , pyrrolyl group, imidazolyl group, pyridyl group, pyrimidinyl group, indolinyl group, isoindolinyl group, indolyl group, isoindolyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, etc., and halogen atoms (chlorine atom, bromine atom) as substituents. , fluorine atom), cyano group, nitro group, trifluoromethyl group, phenyl group, tolyl group, benzyl group, phenethyl group, linear or branched alkyl group having 1 to 5 carbon atoms, 1 to 3 (2 or 3 substitutions!!! When one group is bonded,
The substituents may be the same or different from each other, and include industrial value groups.

When R' and RZ or R3 and R4 are connected, examples thereof include trimethylene group, tetramethylene group, pentamethylene group, oxydiethylene group (-CHz
-CHz 0-CHt-CHz-), and 1 to 3 of the hydrogen atoms of these divalent groups are halogen atoms (chlorine atom, bromine atom, fluorine atom), cyano group, nitro group, phenyl group, tolyl group , a benzyl group, a phenethyl group, and a divalent group substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. Further, the component of these divalent groups may be a part of an aryl ring or a heterocycle.

When R7 is a divalent arylene group, a specific example is p
-phenylene group, m-phenylene S, O-phenylene!
, 1.4-naphthylene 1,2.3-naphthylene group, 4,
A 4'-biferrylene group is mentioned. Examples of polymethylene groups include polymethylene groups having 1 to 22 carbon atoms. In the case of alkylene groups, propylene group, butylene group, pentylidene group, 1,2-dimethylethylene group, 1
゜3-dimethyltrimethylene group, 1,4-dimethyltetramethylene group, 1,5-dimethylpentamethylene group, 1
．． Examples include 6-dimethylhexamethylene group, 1-ethylethylene group, and 1,2-diethylethylene group.

The arylene group and the aralkylene group may be substituted with a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, and an alkyl group having 1 to 5 carbon atoms. .

When R@ is an unsubstituted or substituted li group derived from an alkyl group, an aryl group, or a heterocycle, the above-mentioned R1 is derived from an unsubstituted or substituted alkyl group, aryl group, or heterocycle. represents a group similar to the monovalent group given above.

When R1 is an alkoxy group or a substituted alkoxy group, examples thereof include the aforementioned alkyl group or an alkoxy group having a substituted alkyl group or a substituted alkoxy group.

When R1 is a substituted or unsubstituted monocyclic or bicyclic aryloxy group, examples thereof include the above-mentioned aryloxy group having a substituted or unsubstituted monocyclic or bicyclic aryl group. .

R9 and RI@ represent an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent, and these groups are substituted. When present, substituents include alkyl groups,
Cyano group, hydroxy group, carboxyl group, nitro group,
Halogen atoms such as chlorine, fluorine, bromine, amino groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, acyloxy groups, alkyl groups or amino groups substituted with aryl or aralkyl groups, trifluoro Examples include methyl group.

Specific examples of Re and R11 include methyl group, ethyl group,
n-propyl aLtso-propyl group, n-butyl group,
Straight chain alkyl groups, branched alkyl groups such as 5aC-butyl group, n-hexyl group, 2-ethylhexyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, perfluoroalkyl group, methoxymethyl group, cyanomethyl group group, substituted alkyl group, phenyl group, p-trifluoromethylphenyl group, 0-)lifluoromethylphenyl group, p-cyanophenyl group, 0-cyanophenyl L p-nitrophenyl alt% O-nitrophenyl group , p-bromophenyl li% 0-7m1 Mophenyl aE, p, -chlorophenyl 55, o-chlorophenyl L p-fluorophenyl 5, o-fluorophenyl group, N, N-dimethylamide group, N.

N-diethylamide group, p-carboxylphenyl group,
p-methoxyphenyl group, O-methoxyphenyl group, N
, N-diethylaminophenyl group, N, N-diphenylaminophenyl group, N, N-diethylaminophenyl group, N, N-dimethylphenyl group, naphthyl group, methoxynaphthyl group, N, N-diethylaminonaphthyl group,
Benzyl group, p-bromobenzyl group, p-cyanobenzyl group, p-nitrobenzyl group, p-1-lifluoromethylbenzyl group, O-bromobenzyl group, O-cyanohensyl group, O-nitrobenzyl group, phenylethyl base, 3
Examples include aryl groups such as -phenylpropyl group, p-chlorobenzyl group, and naphthylmethyl group, substituent aryl groups, aralkyl groups, and substituted aralkyl groups. R9
and R+o may be the same or different groups.

RI + represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent; When the group or aralkyl group is substituted, examples of one substituent include R'' and R1
The same substituents listed as the substituents for 8 can be mentioned. Specific examples of R9 and R'' include a hydrogen atom, methyl group, ethyl group, n-propyl a, +30-propyl group, n-butyl group, 5ec-butyl group, n-hexyl group,
Straight chain alkyl groups such as 2-ethylhexyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, perfluoroalkyl group, methoxymethyl group, cyanomethyl group, branched alkyl group, substituted alkyl group, and phenyl group, p-1-lifluoromethylphenyl group, o-
Trifluoromethylphenyl group, p-cyanophenyl L
O-cya/phenyl group, p-nitrophenyl i, o-
nido o phenyl/1z group, p-7' romophenyl group, o
-7' romophenyl group, p-chlorophenyl group, o-chlorophenyl L p-fluorophenyl 75, o-fluorophenyl group, N,N-dimethylamide group, N,N-
diethylamide group, p-carboxylphenyl group, p-
Methoxyphenyl group, 0-methoxyphenyl group, N, N
-diethylaminophenyl group, N,N-diphenylaminophenyl LN.

N-dibenzylaminophenyl group, N,N-dimethylaminophenyl group, naphthyl group, methoxynaphthyl group, cyanonaphthyl group, nitronaphthyl group, chloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, trifluoromethylnaphthyl group, N.

N-diethylaminonaphthyl group, benzyl group, phenylethyl group, 3-phenylpropyl Lp-chlorobenzyl group, p-j lomobenzyl Lp-cyanobenzyl L p-
Nitrobenzyl M, p-trifluoromethylbenzyl 4
, o-bromobenzyl group, 0-cyanobenzyl group, 0-
Examples include aryl groups such as nitrobenzyl groups and naphthylmethyl groups, substituted aryl groups, aralkyl groups, and monosubstituted aralkyl groups.

Ar1 represents a monovalent aromatic hydrocarbon group that may have a substituent or a monovalent heterocyclic group that may have a substituent; in this case, the aromatic hydrocarbon group or the heterocycle Groups include phenyl, naphthyl, anthranyl, furan, virol, thiophene, indole, benzofuran, benzothiofuran, oxazole, imidazole, thiazole, isoxazole, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, phthalazine and These y! :'One body, for example,
2-thio-4-thiazolidinone, 3-pyrazolidinone,
5-Isoxacilone, 2-oxazolidone, 2,4-
Examples include thiazolidinedione, 2-thiophenone, 2-furanone, and 4-pyrimidone. When these have substituents, the substituents include methyl group, ethyl group, n
-propyl group, 1so-propyl group, n-butyl group, 5
Straight chain alkyl groups such as ec-butyl group, n-hexyl group, 2-ethylhexyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, perfluoroalkyl group, methoxymethyl group, cyanmethyl group, branched Alkyl group 2.1-substituted alkyl group, and phenyl L p-trifluoromethylphenyl group, 〇-cyanophenyl group,
p-nitrophenyl group, p-bromophenyl group, O-bromophenyl group, 0-chlorophenyl group, p-fluorophenyl group, p-methoxyphenyl L N, N-diethylaminophenyl group, N, N-dimethylamino Phenyl group, naphthyl group, methoxynaphthyl group, cyanonaphthyl group, chloronaphthyl group, benzyl group, phenylethyl group,
3-phenylpropyl group, p-chlorobenzyl L p-
Aryl groups such as cyanobenzyl group, p-nitrobenzyl Lp-trifluoromethylbenzyl group, O-bromobenzyl group, 0-cyanobenzyl group, 0-nitrobenzyl group, naphthylmethyl group, mono-substituted aryl group, aralkyl group, Substituted aralkyl group, cyano group, hydroxy group, carboxyl group, nitro group, halogen atom such as chlorine, fluorine, bromine, etc., group represented by -NHCOR (R” is substituted or unsubstituted alkyl group, aryl group, aralkyl group) (represents a group), -NH3O□R1ff (R17 has the same meaning as above), SOR"(R" has the same meaning as above), -5ozR"
(R1' has the same meaning as above), -CORI? (R" has the same meaning as above), may be different and has the same meaning as hydrogen atom, substituted or non-monosubstituted alkyl group, aryl group, aralkyl group), sulfone Examples include amino groups substituted with acid groups, amino groups, alkoxy groups, aryl groups, aryloxy groups, alkoxycarbonyl groups, acyloxy groups, alkyl groups, aryl groups, or aralkyl groups, amide groups, trifluoromethyl groups, etc. Yes, these 1
As the substituent, an electron-withdrawing substituent is preferably used rather than a hydrogen atom.

Next, the compound represented by the general formula (■) will be explained in more detail.

R+z and R1'' include an alkyl group with or without a substituent, a group with or without a substituent, and this is the same group as the above-mentioned group represented by R1.

Hydrogen atoms, halogen atoms, (chlorine atoms, bromine atoms, fluorine atoms, etc.), alkoxy groups having 1 to 12 carbon atoms (for example, methoxy groups, ethoxy groups, propoxy groups, butoxy groups, octyl groups, benzyloxy groups, etc.) , carbon number 1-12
an aralkyloxy group (eg, hensyloxy group, phenethyloxy group, etc.).

Specific examples of R14 include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and an aryl group with or without a substituent. The aryl group having a substituent is the above-mentioned R
'2. This is the same group as the aryl group having a substituent represented by R13.

RI5 includes an alkyl group with or without a substituent, and Wl, an aryl group with or without a substituent;
It is a group similar to an unsubstituted or substituted alkyl group and an unsubstituted or substituted aryl group.

Art is an aromatic hydrocarbon group such as phenyl, naphthyl, anthryl, 2-furyl group, 2-thienyl group, 1
-Methyl-2-pyrrolyl group, 5-methyl-2-thienyl group, 2-pyridyl group, 2-benzo(d)thienyl group, 2
-naphtho(2,,3-b)thienyl group, 9-ethylcarbazol-2-yl group, dibenzothiophen-2-yl group, 2-2enoxathiinyl group, 10-ethylphenoxazin-3-yl group, 10- Ethylphenothiazine-3
-Represents a heterocyclic group such as yl group.

These may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, and a substituted amino group.

Specific examples of substituents for Art include those having 1 to 12 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, and hexyl group.
The alkyl group, and the alkoxy group or aralkyloxy group include an alkoxy group having 1 to 12 carbon atoms and an aralkyloxy group having a carbon number, and specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, octyl group. There are oxy groups and benzyloxy groups.

In the case of substituted amino groups, R16 and R1? Examples include an alkyl group having 1 to 12 carbon atoms without one substituent, such as a methyl group, ethyl group, propyl group, or butyl group, or an alkyl group having 1 to 12 carbon atoms having the following substituents.

Represents a substituted or substituted phenyl group, Ruh and R1
may be linked to form a heterocycle.

RI6 and R1? Examples of the substituent of the alkyl group having a substituent represented by include an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a hydroxy group, an aryl group having 6 to 12 carbon atoms, a cyano group, and a halogen atom. and so on.

Specific examples of alkyl groups having substituents represented by R16 and R'7 include alkoxyalkyl groups (e.g., methoxymethyl group, methoxytyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropoxy group, methoxytyl group, propoxymethyl group) etc.), aryloxyalkyl groups (e.g. phenoxymethyl group, phenoxyethyl group, naphthoxymethyl group, phenoxypentyl group, etc.),
Hydroxyalkyl groups (e.g. hydroxymethyl group, hydroxypropyl group, hydroxyoctyl group, etc.), aralkyl groups (e.g. benzyl group, phenethyl group, ω, ω-
diphenylalkyl group, etc.), cyanoalkyl group (e.g. cyanmethyl group, cyanethyl group, cyanopropyl group,
Preferred are cyanobutyl group, etc.) haloal group (eg, chloromethyl group, bromomethyl group, chloroethyl group, bromopentyl group, chlorooctyl group, etc.).

The phenyl group represented by R1& and R1ff may have a substituent, and specific examples of the substituent in the case of a phenyl group having a substituent include an alkyl group having 1 to 12 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. alkoxy group, aryloxy group having 6 to 7 carbon atoms, acyl group having 2 to 8 carbon atoms, 2 to 5 carbon atoms
alkoxycarbonyl group, halogen atom, carbon number 1-
Examples include a monoalkylamino group substituted with an alkyl group having 4 carbon atoms, a dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, an amide group having 2 to 4 carbon atoms, and a nitro group.

As an alkyl group having 1 to 12 carbon atoms, a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, as an alkoxy group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, Propoxy group, butoxy group, phenoxy group as aryloxy group, o-lm-
or P-)lyloxy group, an acetyl group, a propionyl group, a benzoyl group, a 0-5m- or p-toluoyl group as an acyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group as an alkoxycarbonyl group having 2 to 5 carbon atoms; group, butoxycarbonyl group, chlorine atom, bromine atom, fluorine atom as a halogen atom, methylamino group, ethylamino group, butylamino group, carbon number as a monoalkylamino group substituted with an alkyl group having 1 to 4 carbon atoms. Dimethylamino group as a dialkylamino group substituted with 1 to 4 alkyl groups,
Diethylamino group, dipropylamino group, dibutylamino group, N-methyl-N-ethylamino group, amide group such as acetamido group and propionamide group, and other substituents include nitro group.

In addition, RI& and RI7 may be connected to form a heterocycle, and examples of the heterocycle in this case include a pyrrolidino ring, a morpholino ring, an N-methylpiperazino ring, and a gelolidino ring.

Next, specific examples of the exemplified compound 5 compound shown in the above formula (1) (Vl) are shown below, but the present invention is not limited to these compounds.

Exemplary compound 1 Exemplary compound 6 Exemplary compound 2 Exemplary compound 7 ○ Exemplary compound 3 Exemplary compound 8 Exemplary compound 4 Exemplary compound 9 Exemplary compound 1゜ Exemplary compound 15 Exemplary compound 11!11 Example compound cutting 6 ○ Exemplary compound 12 Exemplary compound 17 Exemplary compound @IJ13 Exemplary compound 1 day Exemplary compound 14 Exemplary compound 19 Exemplary compound 20 O Exemplary compound 21 Exemplary compound 22 Exemplary compound 23 Exemplary compound 24 Exemplary compound 30 Exemplified compound 31 Exemplary compound 33 Exemplary compound 34 Exemplary compound 25 Exemplary compound 26 Exemplary compound 27 Exemplary compound 2 days Exemplary compound 29 Exemplary compound 35 Exemplary compound 36 Exemplary compound 37 Exemplary compound 38 Exemplary compound 39 Exemplary compound 40 Exemplified compound 41 Exemplary compound 42 Exemplified compound 43 Exemplary compound 4 days Exemplified Chew 49 Exemplary compound 50 Exemplary compound 51 Exemplary compound 44 Exemplary compound 45 Exemplary compound 46 Exemplary compound 47 Exemplary compound 52 Exemplary compound @J53 Exemplary compound 54 Exemplary compound 56 Exemplified compound 57 Exemplary compound 58 Exemplified compound 62 Exemplary compound 63 Exemplary compound 64 Exemplified compound 59 Exemplary compound 60 Exemplary compound vyJ61 Exemplary compound 65 Exemplary compound 66 Exemplified compound 69 CH3 Exemplary compound’! ! 7167 Exemplary compound 71 Next, the general formula (■) Specific examples of compounds represented by is shown below.

Exemplary compound 68 Exemplified compound 72 CH3 Exemplary compound 73 Exemplary compound 77 CH) Exemplary compound 74 Exemplary compound 7 days Exemplary compound 75 C1(.

Exemplified Compound 76 L Hff Exemplified Compound 81 CZ II 5 Exemplified Compound 82 Exemplified Compound 83 i13 H3 Exemplified Compound 84 Hs In the present invention, the urea and thiourea compounds represented by the general formula N) or -ritual (II) are all 'J, chel
It can be easily synthesized by the method described in Il, Soe, J, Vol. 955, 1571-1581.

Moreover, amides represented by -S formulas (lit) to (IV),
All thioamide compounds are rBeilsteins.
llandbuchderOrganichen Ch
It can be easily synthesized by the method described in Emie J Vol. 12, p. 265.

Furthermore, the (thio)barbic acid compound represented by -ritual (Vl) can be expressed as rorganic Reactions
Kno described in J No. 15S, pages 204-599
By the evenagel condensation method, the corresponding aldehyde or ketone and barbylic acid or thiobarbylic acid are easily dehydrated and condensed using an alkali (e.g., NaOH, KOH, ammonia, amine (e.g., diethylamine, triethylamine, piperidine, etc.)) as a catalyst. can be manufactured.

Furthermore, the hydrazone compound represented by the general formula (■) can be easily synthesized by the method described in JP-A-57-148749.

It is known that an electrophotographic photoreceptor using a phthalocyanine pigment exhibits an indaracyan effect, which causes a delay in the decay of the surface potential immediately after irradiation with light, and this is the origin of the problem. 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. The compound of the present invention is considered to be an aggravating agent for reducing this indaracin-3 effect, shortening the time during which the surface potential does not decay (induction period), and improving sensitivity as a result.

General formulas (1) to (Vl
) is disclosed in Japanese Unexamined Patent Application Publication No. 58-10
No. 2239, No. 58-102240, JP-A-58-6
No. 5438, No. 58-65439, JP-A No. 56-14
This is described in No. 9462 and No. 57-29650.

However, these are claimed to be inventions as exacerbating agents for further sensitizing dye-sensitized organic photoconductors, and do not apply to photoconductors that are not dye-sensitized like the present invention. Furthermore, the specification does not describe the use of a phthalocyanine pigment, which is a photoconductive pigment in the present invention. Z, which is a conductive pigment
Although there is a description of using n○, these are only known to be effective when an inorganic photoconductor such as Zn○ is dye-sensitized, and it is not recommended to use phthalocyanine pigments as in the present invention. It was completely unexpected that it would have the effect of reducing the specific induction effect.

Also, Japanese Patent Publication No. 58-102239, 1982-10224
No. 0, Etsukai No. 58-65438, No. 58-65439
No., JP-A-56-149462, JP-A No. 57-29650
The electrophotographic photoreceptor described in the above issue exhibits good electrophotographic properties when used only once, but after repeated use several times, the electrophotographic photoreceptor described in It cannot be used as a photoreceptor for copiers and optical printers which are used repeatedly.

In addition, when various additives such as tetranitrofluorene, tetracyanoethylene, and other electron-withdrawing compounds are added to increase the sensitivity of phthalocyanine, the chargeability decreases, and upon repeated use, the charging potential decreases and the residual potential increases. occurs.

However, the compounds represented by the general formulas (1) to (VT) of the present invention do not cause the above-mentioned deterioration of repeatability and sensitize phthalocyanine, so they are used for copying that requires high sensitivity and good repeatability. Suitable for use in photoreceptors for machines and optical printers.

The electrophotographic photoreceptor of the present invention grows a photoconductive layer containing the above-mentioned phthalocyanine pigment, - at least one of the compounds represented by formats (I) to (Vl), and - the compound represented by format (■). .

Various types of birch are known as electrophotographic photoreceptors, but
The electrophotographic photoreceptor of the present invention may be any type of photoreceptor.9 Usually, the electrophotographic photoreceptor of the present invention is used in the type of layer structure exemplified below.

(1) A monolayer light guide containing a phthalocyanine pigment, one of the compounds represented by formulas (I) to (Vl), and a compound represented by the -formula (■) is provided on a conductive support. Something.

(2) Phthalocyanine pigment and general formula (
1) A charge generation layer containing a compound represented by formula (VI) is provided, and a charge transport layer containing a compound represented by general formula (■) is provided thereon.

(3) A charge transport layer containing a compound represented by the general formula (■) is provided on a conductive support, and a charge transport layer containing a phthalocyanine pigment and a compound represented by the general formulas (f) to (Vl) is provided thereon. A generation layer is provided.

In order to create an electrophotographic photoreceptor of type (11), - compounds represented by formats (1) to (Vl) and -S formula (■)
The phthalocyanine pigment may be dispersed in a solution containing the compound represented by the formula and the binder, and this may be coated on a conductive support and dried. Alternatively, the phthalocyanine pigment may be dispersed in a binder solution, and then a general method may be applied to this solution. Compounds represented by formulas (1) to (Vl), and -
A coating liquid may be prepared by dissolving a compound represented by the formula (■).

At this time, the thickness of the light guiding layer is 3 to 50μ, preferably 5 to 50μ.
30μ is good.

To create an electrophotographic photoreceptor of type (2), first, phthalocyanine and general formulas (1) to
A charge stopper 1 is provided by dispersing the compound represented by (V[) in a suitable solvent or, if necessary, in a solvent in which a binder has been dissolved, and then coating and drying. Alternatively, a coating solution is prepared by dispersing the phthalocyanine pigment in a solvent or a solvent in which a binder is dissolved, and then dissolving a compound represented by a compound represented by formulas (I) to (Vl>). After that, a solution containing a charge transporting compound represented by the form (■) and a binder is applied thereon and dried to form a charge transporting layer.

The thickness of the charge generation layer at this time is 4μ or less, especially 0.1 to 2μ.
μ is preferable, and the thickness of the charge transport layer is 3 to 50 μ, especially 5 μ.
~30μ is preferred.

Further, in the charge generation layer of the present invention, a thin layer containing a compound represented by a compound represented by -format <1) to (VT) is provided between the charge generation layer and the conductive support, and a A method in which a charge generation layer of a phthalocyanine pigment is provided by deposition, and the phthalocyanine pigment and a compound represented by the general formulas (I) to (VT) are incorporated as a result by diffusion of an upper layer coating solvent, or on a conductive support. It can be produced by depositing a phthalocyanine pigment thereon, applying thereon a solution containing a compound represented by the general formulas (1) to (VT), and allowing the compound to coexist with the phthalocyanine pigment. In this case, the thickness of the phthalocyanine pigment deposited is 0.001μ~
1μ, especially 0.01μ to 0.5μ is preferred.

The electrophotographic photoreceptor of type (3) is produced by reversing the stacking order of the charge generation layer and charge transport layer of type (2).

The type (1) photoreceptor of the present invention has relatively good repeating characteristics because the phthalocyanine itself has a charge transfer ability compared to azo pigments, etc.;
) and (3), the photoreceptors are less sensitive, and the decrease in charging potential and increase in residual potential due to repeated use are also somewhat large.

Therefore, types (2) and (3) are preferable as the usage form of the present invention, and in this form, it has extremely high sensitivity, has little change in the band position in repeated use, has low residual potential, and has a high rigidity resistance. , a highly durable electrophotographic photoreceptor can be obtained.

The phthalocyanine pigment used in photoreceptors of type fil f21 and (3) is pulverized and dispersed using a known dispersion machine such as a ball mill, sand mill, vibration mill, etc. 0
．． It is used after being ground to 1 to 2 microns.

If the amount of phthalocyanine pigment used in the type fi+ electrophotographic photoreceptor is too small, the sensitivity will be poor, and if it is too large, the charging property will be poor and the strength of the electrophotographic photosensitive layer will be weakened. The proportion of the phthalocyanine pigment is 0.01 to 2 times the weight of the binder.
Preferably it is 0.05 to 1 times the weight.

The ratio of the charge transport compound represented by the general formula (■) to the binder is 0.1 to 2 times, preferably 0.3 to 1 times
．． A range of 3 times the weight is good.

The content of the compounds represented by formulas (1) to (VT) is suitably in the range of 0.01 to 1 times the weight of the phthalocyanine pigment, preferably 0.02 to 0.4 times the weight of the phthalocyanine pigment.

In addition, when forming a phthalocyanine compound-containing layer that becomes a charge generation layer in types (2) and (3) electrophotographic photoreceptors, the amount of phthalocyanine pigment used is preferably 0.1 to 50 times the weight of the binder resin or less. In this case, sufficient photosensitivity cannot be obtained.The ratio of the charge transport compound represented by the general formula (■) in the charge transport medium is 0.01 to 10 times the weight of the binder, preferably 0.2 to 2 times the weight of the binder.
Double weight is preferred.

In this case as well, the content of the compounds represented by the general formulas <1) to (Vl) is 0.0% relative to the phthalocyanine pigment.
A suitable range is 1 to 1 times by weight, preferably 0.02 to 0.4 times by weight.

In addition, in photoconductors of type (2) and (3),
0-196767, JP-A-60-254045, and JP-A-60-262159, a charge transporting compound such as a hydrazone compound or an oxime compound may be added to the charge generation layer. You can also do it.

The conductive support used in the electrophotographic photoreceptor of the present invention is a metal plate made of aluminum, copper, zinc, stainless steel, etc., a metal drum, or a sheet or cylindrical substrate made of plastic, paper, etc. Materials that have been vapor-deposited or dispersed coated with conductive materials such as Injem, SnOx, and carbon, or have been provided with conductive polymers, or have been treated with conductive treatment using inorganic salts such as sodium chloride, calcium chloride, or organic quaternary ammonium salts. Used are paper tubes, phenol resin drums molded with carbon, Bakelite drums, etc.

The binder used in the charge generation layer of types (2) and (3) of the present invention can be selected from a wide range of insulating resins, such as polyester resins, cellulose resins, acrylic resins, polyamide resins, polyvinyl butyral resins, Phenoxy resin, polyvinyl formal resin,
Examples include, but are not limited to, polycarbonate resin, styrene resin, polybutadiene resin, polyurethane resin, epoxy resin, silicone resin, vinyl chloride resin, vinyl chloride-vinyl acetate resin, and the like.

As the binder used in 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.

Examples of such high molecular weight polymers include, but are not limited to, the following.

Polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, chloride vinyl
Vinyl acetate-maleic anhydride copolymer, silicone resin,
Examples include silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, and poly-N-vinylcarbazole.

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, chlorinated biphenyl, O-terphenyl, p-terphenyl, cyphthyl phthalate, dimethyl glycol phthalate, dioctyl phthalate,
Triphenyl phosphoric acid, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene,
dilauryl thiodipropionate, 3.5-dinitrosalicylic acid, dimethyl phthalate, dibutyl phthalate,
Examples include diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methyl phthalyl ethyl glycolate, various fluorohydrocarbons, and the like.

In addition, silicone oil or the like may be added to improve the surface properties of the electrophotographic photoreceptor.

Sensitizers include chloranil, tetracyanoethylene,
Methylbioleft, rhodamine B, cyanine dye, merocyanine dye, biryllium dye, thiapyrylium dye, compounds described in JP-A-58-65439, JP-A-58-102239, JP-A-58-129439, JP-A-62-71965, etc. can be mentioned.

As a coating solvent, alcohol M (e.g. methanol,
ethanol, impropatul, etc.), ketones M (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), amides R (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 (for example, methylene chloride, chloroform, methylchloroform, carbon tetrachloride, monochlorobenzene, dichlorobenzene, etc.) can be used singly or in combination.

Application can be carried out using general-purpose coating methods such as spraying, roller coating, spinner coating, blade coating, and date coating.

Further, in the present invention, an adhesive layer or a barrier layer can be provided between the conductive support and the photoconductive layer, if necessary. Materials used for these layers include, in addition to the high molecular weight polymer used for the binder, gelatin, casein, polyvinyl alcohol, ethylcellulose, carboquine-methylcellulose, and JP-A-59-84247.
vinylidene chloride-based polymer latex described in JP-A-59-114544, aluminum oxide, etc., and the thickness of these layers is preferably 0°1 to 5 μm. .

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, the matting agent may include silicon dioxide, glass particles, alumina, starch, or titanium oxide. , particles of polymers such as zinc oxide, polymethyl methacrylate, polystyrene, phenolic resins,
and U.S. Patent No. 2,701,245, U.S. Patent No. 2.99.
2.101 are included. 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 sensitivity, little change in charging potential during repeated use, low residual potential, high rigidity, and excellent durability. be.

The electrophotographic photoreceptor of the present invention can be widely applied to photoreceptors for printers using lasers and cathode ray tubes as light sources, as well as electrophotographic copying machines.

Since it has high sensitivity particularly in the long wavelength range, it is suitable for laser beam printers using semiconductor lasers, He--Ne lasers, etc. as light sources.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the Examples. In the examples, "parts" indicate "parts by weight."

Example 1 ε-type copper fucrocyanine (Liophon 1-EPPC: manufactured by Toyo Ink Co., Ltd.) 0.5 parts Exemplary compound (1) 0.05 parts Polyester resin (Vylon 200: manufactured by Toyobo Co., Ltd.) 3. 0 parts Exemplary Compound (73) 3.0 parts Tetrahydrofuran 100 parts were placed in a 500-glass container together with glass beads, and dispersed for 60 minutes using a paint shaker (Toyo Seiki Seisakusho Co., Ltd.).
The glass beads were filtered to obtain a photoconductive layer dispersion.

Next, using this bone dispersion liquid wire round rod for light guide Ti, it was coated on a conductive support (a 75 μm polyethylene terephthalate film with a vapor-deposited aluminum film on the surface. Surface resistance: 103 Ω), dried, and dried to 20 μm.
An electrophotographic photoreceptor having a photoconductive layer of m was obtained.

Next, the electrical properties of the produced electrophotographic photoreceptor were determined using EPA-8
100 (manufactured by Kawaguchi Electric Co., Ltd.) by static method. The measurement was carried out under the conditions of corona charging with OkV, monochromatic light of 780 parts m], and exposure with a light intensity of mw/rd. Surface potential immediately after charging (■.), 1 immediately after charging
The ratio of the surface potential after 0 seconds to V is called the charge retention rate (DD
,. ), and in terms of sensitivity, the surface potential before exposure is attenuated by light and is halved by exposure! ! The exposure amount (E 9°) is 1/10 of (Es.), and the exposure amount is 10 as the residual potential (■,).
Examining the surface potential at 0 μJ/c4 shows ■.
+667■ ES, 2.1μJ/ct E,, , 1.8μJ/crADD,,
It was 76%v, +19V.

Comparative Example 1 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 1, except that Exemplified Compound (1) was removed from the photoconductive layer coating solution of Example 1. The electrical properties of this electrophotographic photoreceptor were measured under the same conditions as in Example 1. +695■ Eso 2.7 μJ/d E,. It was 8.1μJ/cd DD, 79% V, +41V.

Example 2 3 parts of ε-type copper phthalocyanine (Liophoton EPPC), 0.3 parts of exemplified compound (1), and polyester resin (
After dispersing in a ball mill for 20 hours with a solution of 3 parts of Byron 200) dissolved in 100 parts of lahitorofuran,
Using a wire round rod, it was applied onto a conductive support (the above-mentioned AN vapor-deposited film) and dried to obtain a charge generation layer with a thickness of 0.5 μm.

Next, on the charge generation layer, 10 parts of exemplified compound (70) and a polycarbonate of bisphenol A were added as a charge transport material.
7 parts of 1.10 parts were dissolved in 50 parts of dichloromethane? Contents: Using a wire round iron, the coating was coated and dried to form a charge transport layer with a thickness of 20 μm to prepare an electrophotographic photoreceptor. The electrical characteristics of this electrophotographic photoreceptor are
As a result of measurement under the same conditions as in Example 1 except that corona charging was performed at kv, the result was Vo -753V E. 1.5 μ, J/ct E,. 2.8 μJ/ci DD. The voltage was 73% V -20V. Thereafter, 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 2 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2, except that Exemplary Compound (1) of Example 2 was removed.

The electrical characteristics of this electrophotographic photoreceptor were measured under the same conditions as in Example 2, and found to be Vo 767 V. 2.3 μJ/c E,. 6.5 μJ/cA DD. It was 79% v, -33V.

Comparative Examples 3 and 4 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 2, except that the following comparative compound was used in place of Exemplified Compound (70) as a charge transport material, and its electrical properties were measured.

The results are shown in Table 1.

Comparative Compound (2) Table 1 Example 3 ε-type copper phthalocyanine (Liophorn E) of Example 2
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 Co., Ltd.) was used instead of PPC). The electrical characteristics were measured under the same conditions as in Example 2, and the result was -745V. 0.7 μJ/c4 E9G 1. 8 p J/c4DD,,
75% VR13V. Thereafter, the two steps of charging and exposure were repeated for 10,000 times, and the electrical properties were examined, but there was almost no change from the properties before repeating.

Comparative Example 5 An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 3, except that Exemplified Compound (1) of Example 3 was removed.

The electrical properties of this electrophotographic photoreceptor were measured under the same conditions as in Example 2. -756■ Snake. 1.0 μJ/, ff1 E,. 3.5 μJ/d DD. It was 80% Vl -32V.

Example 4 ε-type copper phthalocyanine (Liophoton EP) 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 VC). The electrical properties of this electrophotographic photoreceptor were measured under the same conditions as in Example 2, and the results were as follows. -723■ E,. 0.6 μJ/ci E,. ], 7 μJ/c DD,. It was 73% VR-14V. Thereafter, 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 6 The electrical properties of the electrophotographic photoreceptor were measured under the same conditions as in Example 2 in exactly the same manner as in Example 3 except that the exemplified compound (1) of Example 4 was removed. -758V Eso t, oμJ/c4 E,. 2.9 μJ/cd DD. 78% ■E -20V.

Examples 5 to 25 As a sensitizer, the exemplified compound shown in Table 2 was used instead of the exemplified compound (1) of Example 3, and as a charge transport substance, Example 3 was used.
An electrophotographic photoreceptor was prepared in exactly the same manner as in Example 3, except that the exemplified compounds shown in Table 2 were used in place of exemplified compound (70). The electrical properties of this electrophotographic photoreceptor are shown in Table 2. The electrical properties were measured under the same conditions as in Example 3.

/ / Example 1 and Comparative Example 1, Examples 2, 5-25 and Comparative Example 2-
4. Comparing Example 3 and Comparative Example 5, and Example 4 and Comparative Example 6, it is found that the compound containing the compound represented by the -S formula (■) and the compound represented by the general formulas (1) to (■) The electrophotographic photoreceptor to which the additive was added was compared to the photoreceptor of the comparative example,
It is 1.5 to 2 times more sensitive. Furthermore, it can be seen that there are no large differences in charge type, dark decay, and residual potential, and good electrophotographic properties are maintained. Furthermore, in Example 2, 3.4, i
It was found (IIV2) that the electrical characteristics after repeated use o and ooo times were almost unchanged from the initial characteristics.

As described above, the electrophotographic photoreceptor shown in the examples satisfies the object of the present invention, ``a highly durable electrophotographic photoreceptor that is highly sensitive, has high potential stability during repeated use, and has a low residual potential.'' I can see that it is something.

Claims (2)

[Claims] (1) In an electrophotographic photoreceptor in which a photoconductive layer is provided on a conductive support, the photoconductive layer contains a) a phthalocyanine pigment, b)
Electrophotography for copying machines or optical printers, characterized in that it contains at least one of the compounds represented by general formulas (I) to (VI), and c) at least one of the compounds represented by general formula (VII). Photoreceptor. 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 (IV) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (V) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VII) ▲ Numerical formulas, chemical formulas, There are tables, etc.▼ In the general formulas (I) to (VII), Z represents a sulfur atom or an oxygen atom. R^1, R^2, R^3, R^4, R^5, and R^6 each represent a monovalent group derived from a hydrogen atom, an alkyl group, or a heterocycle, and may be the same or different from each other. . R^
1 and R^2, or R^3 and R^4 may each be connected. In general formula (I), R^1, R^2,
R^3 and R^4 may be linked together to form a bridged ring as a whole. R^7 represents a divalent arylene group, aralkylene group, polymethylene group or alkylene group. R^8 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 (V), two R^8's may be the same or different. R^9 and R^1^0 represent an alkyl group, an aryl group, or an aralkyl group, and R^9 and R^1^0 may be the same or different groups. R^1^1 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Furthermore, Ar_1 and R^1^1 may form a ring. R^1^2 and R^1^3 are an alkyl group, an aryl group,
Represents an alkoxy group, an aralkyloxy group, an amino group, a hydrogen atom, and a halogen atom. These may be the same or different. R^1^4 represents a hydrogen atom, an alkyl group, or an aryl group. R^1^5 represents an alkyl group or a phenyl group. X^1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or represents a methylene group that may be substituted. X^2 represents an atomic group necessary to form a benzene or naphthalene ring. n represents an integer of 0 or 1. Ar_1, Ar_2 are monovalent aromatic hydrocarbon groups or 1
represents a valent heterocyclic group. (2) The electrophotographic photoreceptor for copying machines or optical printers according to claim (1), wherein the copying base or the light source of the optical printer is a laser beam.