JPH03287275A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To prevent the deterioration of the electrifying characteristics after the repeated uses by providing an intermediate layer selected from tin oxide, titan oxide, etc., formed with a vacuum film forming process between a conductive substrate and a photosensitive layer. CONSTITUTION:On the conductive substrate 11, the intermediate layer 13 is provided, then, the photosensitive layer 15 is provide thereon. The intermediate layer 13 formed with the vacuum film forming process is consisting of at least one group selected from tin oxide, titan oxide. In oxide, iron oxide, La oxide, Zn oxide, Be oxide, Ca oxide and Mg oxide. Thus the electropthotographic sensitive body of high sensitivity, with the degradation of the electrostatic changeability characteristics due to the pre-exposure fatigue, no delay of the rise of potential by electrostatically charged potential with lower dark decay can be obtained.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to improvements in electrophotographic photoreceptors. [Prior Art] In recent years, organic photosensitive materials, which have advantages such as low cost, productivity, and non-pollution, have become popular as photoconductors used in electrophotographic copying machines. Organic electrophotographic photoreceptors include photoconductive resins such as polyvinylcarbazole (PVK) and PVKTNF (
There are charge-transfer complex photoreceptors such as 2,4,7-dolinitrofluorenone), pigment-dispersed photoreceptors such as phthalocyanine binders, and functionally separated photoreceptors that use a combination of a charge-generating substance and a charge-transporting substance. In particular, functionally separated type photoreceptors are attracting attention. When such a functionally separated high-sensitivity photoreceptor is applied to the Carlson process, it has low chargeability and poor charge retention characteristics (large dark decay), and these characteristics deteriorate significantly with repeated use, resulting in poor image quality. Moreover, it has disadvantages of density unevenness, fogging, and, in the case of reversal development, background smearing. Furthermore, in general, high-sensitivity photoreceptors have reduced chargeability due to pre-exposure fatigue. This pre-exposure fatigue is mainly caused by light absorbed by charge-generating materials, so the longer the charges generated by light absorption remain in the photoconductor in a mobile state, the greater the number of charges. It is thought that the lower the chargeability due to pre-exposure fatigue becomes, the more the chargeability decreases. In other words, even if a charging operation is performed while charges generated by light absorption remain, the surface charges are neutralized by the movement of the remaining carriers.
The surface potential does not rise until the residual charge is consumed. Therefore, the rise in surface potential is delayed by the amount of pre-exposure fatigue, and the apparent charged potential becomes lower. To solve the above-mentioned drawbacks, for example, JP-A-47-6341゜48-3544 and JP-A-48-12034 have cellulose nitrate resin intermediate layers;
-25638.58-30757.58-63945.
58-95351.58-98739 and 60-66
No. 258 has a nylon resin intermediate layer, which is disclosed in JP-A-4969.
Nos. 332 and 52-10138 disclose a maleic acid resin intermediate layer, and JP-A-58-105155 discloses a polyvinyl alcohol resin intermediate layer. In addition, intermediate layers have been proposed in which various conductive additives are contained in a resin in order to control the electrical resistance of the intermediate layer. For example, JP-A No. 51-65942 uses an intermediate layer in which carbon or chalcogen-based substances are dispersed in a curable resin, and JP-A No. 52-82238 uses an isocyanate-based curing agent with the addition of a quaternary ammonium salt. The thermopolymer intermediate layer
JP-A No. 55-1180451 discloses a resin intermediate layer containing a resistance adjusting agent, JP-A No. 58-58556 discloses a resin intermediate layer containing aluminum or tin oxide dispersed therein, and JP-A No. 58-93062 discloses a resin intermediate layer containing an oxide of aluminum or tin dispersed therein. A resin intermediate layer to which an organometallic compound is added is disclosed in JP-A-58-93063゜60-973.
No. 63 and No. 60-111255 have a resin intermediate layer in which conductive particles are dispersed, and Japanese Patent Application Laid-Open No. 59-84257.5
Nos. 993453 and 60-32054 disclose a resin intermediate layer in which Tie□ and 5n02 powder are dispersed. However, it is still insufficient in terms of deterioration in chargeability due to repeated use, particularly in terms of delay in the rise of charge potential, and further improvements have been desired. [Problems to be Solved by the Invention] The present invention has high sensitivity, significantly reduces charging performance due to pre-exposure fatigue, and has no delay in the rise of charging potential even after repeated charging and exposure, and dark decay. The purpose of the present invention is to provide a small photoreceptor for electrophotography. [Means for Solving the Problem] 3-4- According to the present invention, in an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive substrate, a method for forming a vacuum thin film between the conductive substrate and the photosensitive layer is provided. Tin oxide, titanium oxide, formed by
An electrophotographic photoreceptor is provided that has an intermediate layer made of at least one selected from indium oxide, iron oxide, lanthanum oxide, zinc oxide, beryllium oxide, calcium oxide, and magnesium oxide. An electrophotographic photoreceptor having a highly sensitive photosensitive layer has a strong tendency to cause a delay in the rise of the surface potential during charging and dark decay due to repeated use. On the other hand, in general, when an intermediate layer is provided between a conductive substrate and a photosensitive layer, residual potential is likely to occur, especially when the intermediate layer is made of an insulating material such as a resin. In view of these points, the present inventors have proposed that in an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive substrate, the metal compound formed between the conductive substrate and the photosensitive layer by a vacuum thin film forming method is used. The inventors have discovered that the above problems can be solved by providing an intermediate layer, and have completed the present invention. The present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing an example of the structure of the electrophotographic photoreceptor of the present invention, in which an intermediate JtiJ 13 and then a photosensitive layer 15 are provided on a conductive substrate 11. FIG. 2 is a sectional view showing another configuration example of the present invention. The photosensitive layers are stacked in this order: a charge generation layer 17 and a charge transport layer 19. FIG. 3 is a cross-sectional view showing yet another configuration example. The photosensitive layers are stacked in this order: a charge transport layer 19 and a charge generation layer M17. FIG. 4, FIG. 5, and FIG. 6 are sectional views showing yet another example of the configuration. A protective layer 21 is provided on the structures shown in FIGS. 1, 2, and 3, respectively. Next, the intermediate layer 13 will be explained. The intermediate layer is a layer made of the metal compound described above and formed on the conductive substrate 11 by a vacuum thin film forming method. The thickness of the intermediate layer used in the present invention is 100 to 10-1
Preferably 500 people to 5

[is. Vacuum thin film creation methods include resistance heating and ion beam heating.
vacuum evaporation method, sputtering method, 5-6-reactive sputtering method, ion blating method, M
Conventionally known methods such as BE and CVD are used. In addition to SnO and SnO2, tin oxide is generally used in 5n20.
. 5n304 etc. are known, and also by vacuum thin film production method.
The formed tin oxide has a composition that deviates from the stoichiometric composition.
Thin films of can also be made. At this time, a film with a composition of 5n02
has a high resistance, and when there is less oxygen, it has a lower resistance.
However, any tin oxide film is not included in the present invention.
It can be suitably used as an interlayer. In addition, antimony etc. are doped into tin oxide for the purpose of lowering the resistance.
copper, aluminum, etc. for the purpose of high resistance.
Doped products are known, but in any case, the present invention
It belongs to the category of , and can be used well. Titanium oxide is generally divalent TiO2 trivalent Ti2O3
, tetravalent Tie, is known, but it is
The formed titanium oxide has a non-stoichiometric composition.
Thin films can also be made with compositions such as: Also in the selection of starting materials
Therefore, it is possible to incorporate hydrogen atoms, carbon atoms, halogen atoms, etc.
In some cases, a solder film is formed, and Zr, Hf, Y, etc.
If a material to which
A titanium oxide thin film is formed. These titanium oxide films
Any of these can be satisfactorily used as the intermediate layer of the present invention. Indium oxide generally consists of monovalent In2O and trivalent In
2O3 is known, and it can also be formed by vacuum thin film production method.
Indium oxide has a composition that deviates from the stoichiometric composition.
thin films can also be created, and any indium oxide film is
It can be suitably used as a bright intermediate layer. Also, indium oxide for the purpose of improving conductivity. Toped with tin, etc., or copper or aluminum for the purpose of high resistance.
There are known ones doped with minium etc., but none of them.
It falls within the scope of the present invention and can be used satisfactorily. Generally, iron oxides are Fed, Fe2O3, Fe3O4
etc. are well known, but they are formed using the vacuum thin film creation method.
In iron oxide, the composition deviates from the stoichiometric composition.
Membranes may also be made, both of which work well as intermediate layers in the present invention.
Can be used. 7- Lanthanum oxide is generally known as trivalent La203.
However, the lanthanum oxide produced using the vacuum thin film production method
Therefore, thin films with compositions that deviate from the stoichiometric composition can be created.
, any lanthanum oxide film is suitable as the intermediate layer of the present invention.
Can be used for Zinc oxide is generally expressed as ZnO, but it is difficult to create a vacuum thin film.
In zinc oxide formed by the method, the stoichiometric composition
Thin films with staggered compositions can also be created. Also, depending on the selection of starting materials, hydrogen atoms, halogen
A thin film incorporating atoms, carbon atoms, etc. is formed. this
Both of the zinc oxide films of
used. Beryllium oxide is generally known as BeO, but it is thin in vacuum.
For beryllium oxide formed by film formation method, chemical
Thin films with compositions that deviate from stoichiometric compositions can also be created;
It can also be used satisfactorily as an intermediate layer in the present invention. Calcium oxide is generally known as CaO, but in vacuum
Calcium oxide formed by the thin film method has no chemical reaction.
Thin films with compositions that deviate from the stoichiometric composition can also be created;
Both can be used satisfactorily as the intermediate layer of the present invention. Magnesium oxide is generally known as MgO, but the true
In magnesium oxide formed by the empty thin film method,
, thin films with compositions that deviate from the stoichiometric composition can also be created;
Any of them can be satisfactorily used as the intermediate layer of the present invention. Vacuum thin film creation methods include resistance heating and ion beam heating.
vacuum evaporation method, sputtering method, reactive sputtering method etc.
Taling method, ion blating method, MBE. CV
Any conventionally known method such as D can be adopted, but the intermediate layer type
It is desirable to select the appropriate amount depending on the type of component. For example, tin oxide and indium oxide are used as components for forming the intermediate layer.
Dium, iron oxide, lanthanum oxide, beryllium oxide, oxide
When using calcium and magnesium oxide,
Vacuum deposition method using anti-heating, ion beam, etc., sputtering
Sputtering method, reactive sputtering method, ion blasting method
The chemical vapor deposition method, CVD method, etc. are preferably used. lO− In addition, to create the intermediate layer made of titanium oxide of the present invention,
Resistance using Tie, Tl2O3, and Tin□ as evaporation materials
Vacuum deposition method by anti-heating or electron beam heating, evaporation material
Reactive vapor deposition method using Ti in 02 atmosphere, target
Ti01Ti20. , using Tie2, Ar or
Sputtering method using Ar-0□ or 0□, etc.
Ar-
Reactive sputtering method using 02 or 0□, etc.
Ti, Ti01Ti20. using 0□atm.
Ion blating method under ambient atmosphere, TiCQ4, Ti
Raw material gas such as Br, CO2, o2.1120, etc.
uses a gas diluted with Ar, He, 82, etc.
The CVD method and other known methods can be used. To create the intermediate layer made of zinc oxide of the present invention, a vapor deposition material is used.
Vacuum evaporation method using ZnO, ZnO as target
Spa using Ar or Ar-0□ or 02, etc.
uttering method, using Zn as the evaporation material in a 0□ atmosphere.
Ion blating method, Zn, ZnO1ZnCQ2,
ZnBr2, Zn(c2Hs)2, Zn (ocl(a
)2, Zn (QC211,)2, Zn (OnC3
H7)2, Zn (OnC4H9)2, Zn (Cs
14. o□) 2.0□, raw materials such as N20 or this
using a gas diluted with Ar, He, H2, N2, etc.
The CVD method and other known methods can be used. Also, the reason why the vacuum thin film production method is used is because of the purity of the film.
High strength, ability to form a dense film, and formation of a uniform film
Here are some things you can do. Furthermore, using such an intermediate layer
As a result, the performance of the electrophotographic photoreceptor is improved, and the essential points according to the present invention are improved.
It satisfies the requirements. The intermediate layer created in the above manner is amorphous.
solid solution, crystalline solid, and a mixture of two or more of these.
You can. The conductive support 11 has a volume resistance of 1010Ω (1)
Materials that exhibit the following conductivity, such as aluminum and nickel.
Metals such as kel, chromium, nichrome, copper, silver, gold, platinum, etc.
, metal oxides such as tin oxide, indium oxide, etc.
Or by sputtering to form a film or cylinder.
coated with plastic, paper, etc., or aluminum
minium, aluminum alloy, nickel, stainless steel, etc.
board and 11- 12- glue them, 1. ．． 1.1. , extrusion, drawing, etc.
Tubes that have been surface-treated by cutting, superfinishing, polishing, etc. after being made into raw tubes.
etc. can be used. The photosensitive layer 15 in the present invention may be of a single layer type or a laminated type.
However, for the sake of explanation, we will first discuss the laminated type.
Ru. The charge generation layer 17 is a layer mainly composed of a charge generation substance,
A binder resin may be used if necessary. Inorganic and organic materials are used as charge-generating substances.
can be done. Inorganic materials include crystalline selenium and amorphous
As selenium, selenium-tellurium, selenium-tellurium-halo
Gen, selenium-arsenic compounds, amorphous silicon
etc. In amorphous silicon,
Terminating dangling bonds with hydrogen atoms and halogen atoms
doped with boron atoms, phosphorus atoms, etc.
It is well suited to use. On the other hand, organic materials include phthalocyanine pigments and naphthalene pigments.
Russianine pigments, perylene pigments, perinone pigments,
Quinacridone pigments, quinone fused polycyclic compounds, SQUA
Liric acid dyes, azulenium salt dyes, monoazo pigments
, disazo pigments, trisazo pigments, etc. are used.
Ru. Among these charge-generating substances, especially the following structural formula:
Disazo or trisazo pigments represented by are preferably used.
I can stay. (However, Cp is a coupler residue, and the same applies hereinafter.) 13- 14- (However, R represents a hydrogen atom, an alkyl group, or a) rogen atom. ) (However, A represents a type of NH-1, -8-.) (However, R is a hydrogen atom, a substituted or unsubstituted (however, n represents an integer between 1 and 5) an alkyl group UN-up 15-16 Phenolic hydroxyl groups such as phenols and naphthols
Aromatic amino compounds having an amino group
Or an amino group having an amino group and a phenolic hydroxyl group.
Naphthols, aliphatic or aromatic enolic ketones
Compounds having an active methylene group (compounds having an active methylene group)
etc. are used, preferably the following formulas (1) to (11
). [Formula (1), (2), (3) and (4) above
Inside, X, Yl, Z, m and n are each of the following:
represent These coupler residues Cp represent, for example, an 18-substituted alkyl group, and R3 is a substituted or unsubstituted alkyl group.
Represents an alkyl group or a substituted or unsubstituted aryl group.
Was. ) ■1: Hydrogen, halogen, substituted or unsubstituted alkyl
group, substituted or unsubstituted alkoxy group, carboxy group
, sulfone group, substituted or unsubstituted sulfamoyl group
or -CON-Y24 (R4 is hydrogen, alkyl group or its substituted product, phenyl group
or a substituent thereof, and Y2 is a hydrocarbon ring group or
its substituent, heterocyclic group or its substituent nil or an integer of 2 m: an integer of 1 or 2] [In formulas (5) and (6), R7 is substituted or unsubstituted
represents a hydrocarbon group, and A represents a divalent aromatic hydrocarbon group or
represents a divalent heterocyclic group containing a nitrogen atom in the ring (this
(the rings may be substituted). X is the same as above. ] R5 is a hydrocarbon ring group or its substituted product, a heterocyclic group or
Substituted product thereof or styryl group or substituted product thereof, R6
represents hydrogen, an alkyl group, a phenyl group, or a substituent thereof.
Wasuka or R9 and R6 are the carbons bonded to them
A ring may be formed together with the atoms. ) is shown. ) 2: Hydrocarbon ring or its substituted product or heterocycle Ar. [In the formula, R11 is an alkyl group, a carbamoyl group, a carbo
represents an xy group or its ester, and Ar1 is a hydrocarbon
Represents a ring group or a substituent thereof, and X is the same as above
. ] 19-20- [In the above formulas (8) and (9), Rg is hydrogen or substituted
or represents an unsubstituted hydrocarbon group, and Ar2 is a hydrocarbon group.
Represents a bare ring group or its substituted product. ] Said general formula (1)
, (2), (3) or (4) Z hydrocarbon
Examples of the ring include a benzene ring and a naphthalene ring.
Also, as a heterocycle (which may have substitutions), Indian
ring, carbazole ring, benzolane ring, dibenzofuran
Examples include ring rings. As a substituent in ring 2,
Examples include halogen atoms such as chlorine atoms and bromine atoms. The hydrocarbon ring group in Y2 or R5 is phenyl
Ru group, naphthyl group, anthryl group, pyrenyl group, etc.
In addition, examples of heterocyclic groups include pyridyl group, thienyl group, and free ring group.
group, indolyl group, benzofuranyl group, carbazolyl group
group, dibenzofuranyl group, etc., and furthermore, R6
and the ring formed by bonding R6 with fluorene
An example is a ring. Y2 or R5 hydrocarbon ring group or heterocyclic group or
a substituent in the ring formed by R5 and RG;
methyl group, ethyl group, propyl group, butyl group, etc.
Which alkyl group, methoxy group, ethoxy group, propoxy group
group, alkoxy group such as butyl-oxy group, chlorine atom, bromine
Halogen atoms such as atoms, dimethylamino groups, diethyl
Dialkylamino groups such as amino groups, trifluoromethyl
halomethyl groups such as nitro groups, cyano groups, carboxyl groups, etc.
xyl group or its ester, hydroxyl group, -5o3Na etc.
which sulfonic acid groups, etc. As a substituent for the phenyl group of R4, chlorine atom or bromine
Examples include halogen atoms such as atoms. Representative examples of the hydrocarbon group in R7 or Rg are:
Aluminum groups such as methyl, ethyl, propyl, butyl
Aryl groups such as kill groups and phenyl groups, or their substitution
An example is conversion. 22- As a substituent in the hydrocarbon group of R7 or Rg,
Aluminum groups such as methyl, ethyl, propyl, butyl
Kill group, methoxy group, ethoxy group, propoxy group, but
Alkoxy groups such as xy groups, chlorine atoms, bromine atoms, etc.
Examples include a halogen atom, a hydroxyl group, and a nitro group. The hydrocarbon ring group in Ar1 or Ar2 is
Typical examples are phenyl group, naphthyl group, etc.
Substituents in these groups include methyl group, ethyl group,
group, alkyl group such as propyl group, butyl group, methoxy
groups, ethoxy groups, propoxy groups, butoxy groups, etc.
Halogens such as koxy group, nitro group, chlorine atom, bromine atom, etc.
atom, cyano group, dimethylamino group, diethylamino
Examples include dialkylamino groups such as groups. Furthermore, among X, a hydroxyl group is particularly suitable. Among the above coupler residues, the above-mentioned - formula (
2) , (5) , (6) , (7) , (8
) and (9), among which the general
It is preferable that X in the formula is a hydroxyl group. Also, in this
However, a coupler residue represented by the general formula (10) (yz and 2 are the same as above) is preferable, and more preferable.
or a compound represented by the general formula (z, y2 and R2 are the same as above).
It is a Pupler residue. Furthermore, among the above preferred coupler residues, common
Formula (12) or (13) ゝ2' R5 23- 24- (Z, R2, R5 and RG are the same as above, and
R□. Examples of the substituent include the above-mentioned substituent Y2. )in
expressed. The binder resin used as necessary is polyethylene.
Amide, polyurethane, polyester, epoxy resin,
polyketone, polycarbonate, silicone resin, acrylic
Ryl resin, polyvinyl butyral, polyvinylformer
polyvinyl ketone, polystyrene, poly-N-vinyl
Examples include lucarbazole, polyacrylamide, etc.
. Methods for forming the charge generation layer 17 include vacuum thin film formation method and
A major example is the casting method from a solution dispersion system.
It will be done. The former method includes vacuum evaporation, glow discharge decomposition, and ionization.
emblating method, sputtering method, reactive sputtering method
Taling method, CVD method, etc. are used. As the charge generation N17, the above-mentioned inorganic materials and organic materials can be used.
A material layer can be formed well. In addition, a charge generation layer can be formed using the latter casting method.
In order to
, along with a binder resin if necessary.
Ran, cyclohexanone, dioxane, dichloroethane
, ball mill, attritor using a solvent such as butanone
, disperse with a sand mill, etc., and dilute the dispersion liquid appropriately.
It can be formed by coating with Application is dip coating
This can be done using methods such as spray coating, bead coating, etc.
I can. The thickness of the charge generation layer provided as described above is 0.
Approximately 0.01 to 5 μm, preferably 0.05 to 5 μm.
It is 2H. The charge transport layer 19 includes a charge transport material and a binder resin.
Dissolve or disperse it in a suitable solvent, apply it, and dry it.
It can be formed by Also, if necessary, add plasticizer or resin.
Belling agents and the like may also be added. Charge transport materials include hole transport materials and electron transport materials.
Ru. Examples of electron-transporting substances include chloranyl and bromine.
Muanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4.7-trinitro-
9-fluorenone, 2,4,5.7-tetranitro-9
-Fluorenone, 2,4,5.7-titranitroxane
ton, 2,4°8-trinidrothioxanthone, 2,6
．． 8-trinitro-4H-indeno(1,2-b)thio
Phen-4-one, 1,3.7 trinitrodibenzothio
Electron-accepting substances such as phenone-5,5-dioxide
can be mentioned. As a hole transport material, electrons expressed by the following general formula are used.
Donating substances and the like can be mentioned and are well used. (However, R□ is a lower alkyl group, a lower alkoxy group, or
represents a halogen atom, n represents an integer of O to 4, R
2, R3 may be the same or different, hydrogen atom, low
represents a class alkyl group, lower alkoxy group or halogen atom.
Was. ) (In the formula, R21R3 and R4 are hydrogen atoms, substituted
or represents an unsubstituted aryl group, Ar is a substituted or unsubstituted aryl group;
represents an unsubstituted aryl group, and Ar1 and R1 are common
A ring may be formed, and n is an integer of O or 1. ) (wherein, R1 is an alkyl group having 1 to 11 carbon atoms, substituted or
Represents an unsubstituted phenyl group or heterocyclic residue, R2
, R, may be the same or different, and hydrogen atoms
child, lower alkyl group, C□~04 hydroxyalkyl
group, 01-C4 chloralkyl group, or substituted or
represents an unsubstituted aralkyl group, and R2 and R3 are jointly
may form a nitrogen-containing hetero 27-28- ring, and R4, R, may be the same or different.
hydrogen atom, lower alkyl group, or lower alkyl group.
Represents a alkoxy group or a halogen atom. ) represents a group, R2 is a hydrogen atom, a lower alkyl group, a lower
Represents an alkoxy group, halogen atom or nitro group
, n represents 0 or 1. ) (wherein R1 is a hydrogen atom or
represents a halogen atom, and R2 is a substituted or unsubstituted aromatic atom.
Aromatic residues or heterocyclic residues (however, the above substituents are halogen
cyano, di-lower alkylamino, substituted or unsubstituted
dialkylamino group, lower alkyl group, lower alkoxy group
selected from the group consisting of cy group and nitro group. ) represents
. ) (wherein, R is a carbazolyl group, a pyridyl group, a thienyl group
, indolyl group or furyl group, or each substituted or
or unsubstituted phenyl group, styryl group, naphthyl group or
anthryl group (however, the above substituent is di-lower alkylamino
group, lower alkyl group, lower alkoxy group, halogen atom
, an aralkylamino group, or an amino group.
(to be revealed). ) 2 (wherein R1 and R3 are hydrogen atoms, lower alkyl groups, lower
Alkoxy group, di-lower alkylamine-29 30-, hydrogen atom, lower alkyl group, lower alkoxy group,
Represents a phenyl group, phenoxy group, or halogen atom
. ) (wherein, R1 is a hydrogen atom, a halogen atom, a cyano group, a
represents a class alkyl group, and Ar is (where R2, R,
, R, is a hydrogen atom, a substituted or unsubstituted lower alkyl group
Or represents a substituted or unsubstituted benzyl group, R4,
R is a hydrogen atom, a halogen atom, a lower alkyl group, or
represents a lower alkoxy group or a di-lower alkylamino group.
vinegar. ). ) (In the formula, R□1R21R31R41RG is a hydrogen atom,
rogen atom, lower alkyl group, lower alkoxy group, substitution
or unsubstituted di-lower alkylamino group or dibenzyla
Represents a mino group, R5 is a lower alkyl group or a benzyl group
represents. ) (In the formula, Ar is a naphthalene ring, anthracene ring, styryl ring,
group and their substituents, or pyridine ring, furan
ring, thiophene ring, R is a lower alkyl group or
represents a ndyl group. ) Mouth 1 (In the formula, R□ is a lower alkyl group, 2-hydroxyethyl
group or 2-chloroethyl group, R2 is lower alkyl
represents a hydrogen group, a benzyl group or a phenyl group, and R3 is hydrogen.
Atom, halogen atom, lower alkyl group, lower alkoxy
31-32-1 (wherein R represents a hydrogen atom, a lower alkyl group, a chloroethyl group, or a di-lower alkylamino group or a nitro group)
represents a hydrogen atom or a hydroxyethyl group, and R2 is a hydrogen atom.
or represents a halogen atom, R3 is a lower alkyl group, di
Lower alkylamino group, diarylamino group, substituted or
Unsubstituted styryl group, substituted or unsubstituted aromatic ring residue (aromatic
Aroma ring or benzene ring, naphthalene ring, anthracene ring, etc.
), substituted or unsubstituted heterocyclic residues (heterocycle is a pyridine ring
, quinoxaline ring, carbazole ring, etc.). ) Substituted or unsubstituted heterocyclic residues (heterocycles include pyridine rings, quino rings,
xaline ring, carbazole ring, etc.). ) (In the formula, R1 and R2 may be the same or different, and water
Elementary atoms, lower alkyl groups, hydroxy lower alkyl groups,
Chlor lower alkyl group, alkyl having 1 to 2 carbon atoms
alkyl group, a cycloalkyl group having 5 to 6 carbon atoms,
or represents a substituted or unsubstituted aralkyl group. ) (In the formula, R1 represents a lower alkyl group, R2 represents a lower alkyl group, and R2 represents a lower alkyl group.
Alkyl group, di-lower alkylamino group, diarylamino group
group, substituted or unsubstituted styryl group, substituted or unsubstituted aromatic
Aromatic ring residues (aromatic rings include benzene ring, naphthalene ring, ant
helical ring, etc.), (wherein, R1, R3 and R4 are hydrogen atoms)
child, amino group, alkoxy group, thioalkoxy group, ali
ruoxy group, methylenedioxy group, substituted or unplaced
substituted alkyl group, halogen atom, or substituted or unsubstituted
aryl group, R2 is a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen
represents the However, if R1, R2, R3 and R4 are all
Excludes cases where the hydrogen atom is a hydrogen atom. Also, Q. m and n are integers of 1, 2.3 or 4, each of which is 2,
When the integer is 3 or 4, the above R1, R2, R3 and R4
may be the same or different. A-Ct(□CH□-Ar'-CH2C112-A(formula
Ar" is a substituted or unsubstituted aromatic hydrocarbon group
or a heterocyclic group, A is substituted or unsubstituted N
- substituent: a rubazolyl group or an aromatic hydrocarbon group or a heterocyclic group, R1 and R
2 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group
is an unsubstituted aryl group. ). ) These charge transport substances can be used alone or in combination of two or more.
I can stay. As binder resin, polystyrene, styrene-acrylic
Rylonitrile copolymer, styrene-butadiene copolymer
, styrene-maleic anhydride copolymer, polyester,
Polyvinyl chloride, vinyl chloride vinyl acetate copolymer, polyvinyl chloride
Vinyl acetate, polyvinylidene chloride, polyarylate resin
, phenoxy resin, polycarbonate, cellulose acetate
resin, ethyl cellulose resin, polyvinyl butyral,
Polyvinyl formal, polyvinyl I/luene, poly-
N-vinylcarbazole, acrylic resin, silicone tree
resin, epoxy resin, melamine resin, urethane resin,
Thermoplastic or thermosetting resins such as nord resins and alkyd resins
Examples include polyester resins. Solvents include tel-lahydrofuran, dioxane, and trichlorhydrofuran.
toluene, monochlorobenzene, dichloroethane, methane chloride
Tyrene etc. are used. The appropriate thickness of the charge transport layer 19 is about 5 to 100 μm.
Ru. In addition, in the present invention, plasticization during charge transport J11.7
or a leveling agent may be added. As a plasticizer,
General products such as dibutyl phthalate and dioctyl phthalate
-35 36, which is used as a plasticizer for resins, can be used as is, and the amount used depends on the binder resin.
A suitable amount is about 0 to 30% by weight based on the fat. As a leveling agent, dimethyl silicone oil,
Silicone oil such as tylphenyl silicone oil
polymers with perfluoroalkyl groups in their side chains
Alternatively, oligomers are used, the amount of which is
- Appropriately 0 to 1 weight 2 to resin. Next, the case where the photosensitive layer 15 has a single layer structure will be described. The inorganic photosensitive layer is made of the above-mentioned amorphous selenium or selenium.
Alloys, amorphous silicon photosensitive layers, etc. are also mentioned above.
vacuum evaporation method, glow discharge decomposition method, ion blating method
sputtering method, reactive sputtering method, C
It can be provided by a vacuum thin film forming method such as a VD method. Also
, photoreceptors with two or more layers of these inorganic materials are also developed.
It belongs to the simplification of light. When forming a single photosensitive layer using the casting method, in most cases
Functionally separated type consisting of a charge-generating substance and a charge-transporting substance
can be mentioned. That is, charge generating substances and charge transport substances
The materials mentioned above can be used for the quality. The monolayer photosensitive layer consists of a charge generating material, a charge transporting material and
The binder resin is dissolved or dispersed in a suitable solvent, and this
It can be formed by coating and drying. Also, necessary
It is also possible to add plasticizers, leveling agents, etc.
Ru. As the binder resin, the above mentioned charge transport 119
In addition to using the binder resin as it is, charge generation Ji
The binder resins listed in 17 may be used in combination. A single photosensitive layer consists of a charge generating material, a charge transporting material and a binder.
Add the under resin to Tetra 1 to Rofuran, Dioxane, Dioxane.
Dispersion using solvents such as lolethane and cyclohexanone
The coating liquid dispersed by a machine, etc. is applied by dipping coating method or spray coating.
It can be formed by coating with , bead coating, etc. Pyrylium dye, bisphenol A polycarbonate
A photoreceptor in which a charge transport substance is added to the eutectic complex formed from
It can be formed by The thickness of the single photosensitive layer is suitably about 5 to 100 mm. In addition, in the present invention, a protective layer M21 is further applied on the photosensitive layer.
It is also possible to provide one. The protective layer 21 is provided for the purpose of protecting the surface of the photoreceptor.
Materials used include ABS resin, AC5 resin, and
Refin rubinyl monomer copolymer, chlorinated polyether
resin, allyl resin, phenolic resin, polyacetal, polyester resin,
lyamide, polyamideimide, polyacrylate, poly
Allyl sulfone, polybutylene, polybutylene terephtha
rate, polycarbonate, polyether sulfone, polycarbonate
Polyethylene, polyethylene terephthalate, polyimide
, acrylic resin, polymethylpentene, polypropylene
, polyphenylene oxide, polysulfone, polystyrene
AS resin, butadiene-styrene copolymer, polyurethane
Rethane, polyvinyl chloride, polyvinylidene chloride, epoxy
Examples include resins such as resin. The protective layer also has a wear-resistant
Polytetrafluoroethylene and other materials are used to improve wear resistance.
Unafluororesin, silicone resin, and oxidation to these resins
Dispersion of inorganic materials such as titanium, tin oxide, potassium titanate, etc.
It is possible to add the following. Formation method of protective layer
Then, a conventional coating method is used. The thickness of the protective layer is
A value of about 0.5 to 10 is appropriate. In the present invention, another intermediate layer (
(not shown) may also be provided. In addition, in the present invention, in order to improve environmental resistance,
However, in order to prevent a decrease in sensitivity and an increase in residual potential, acid
Antioxidants can be added. Antioxidants can be added to any layer containing organic matter.
However, good results are obtained when added to a layer containing a charge transport material.
You can get results. The following antioxidants can be used in the present invention:
The following can be mentioned. Monophenolic 2,6-di-t-butyl-P-cresol, butylated hydrogen
Droxyanizole, 2,6-di-t-butyl-4-ethyl
Thirph 39 40-enol, stialyl β-(3,5-di-t-butyl
-4-hydroxyphenyl)propionate and the like. Bisphenol compound 2.2'-methylene-bis-(4-methyl-6-t-butylene)
methylphenol), 2,2'-methylene-bis-(4-
ethyl-6-t-butylphenol), 4,4'-thio
Bis-(3-methyl-6t-butylphenol), 4,
4'-Butylidenebis-(3methyl-6-t-butylph
phenol) etc. Polymeric phenolic compound 1.1.3-tris-(2-methyl-4-hydroxy-
5-t-butylphenyl)butane, 1,3.5-trimethane
Chil-2,4,6-tris(3,5-di-t-butyl-4
-hydroxybenzyl)benzene, tetrakis-[methyl
Ren-3-(3', 5'-di-t-butyl-4'-
Hydroxyphenyl)propione-1-]methane, bis
[3,3'-bis(4'-hydroxy-3'-t-butylene)
(luphenyl) butyric acid coglycol ester
, tocopherols, etc. Para-phenylene diamines N-phenyl-N'-isopropyl-P-phenylene diamines
Amine, N,N'-di-5ec-butyl-p-phenyle
diamine, N-phenyl-N-see-butyl-p-
phenylenediamine, N,N'-diisopropyl-p-
phenylenediamine, N,N'-dimethyl-N,N'-
di-t-butyl-p-phenylenediamine and the like. Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-di-t-octylhydroquinone
Dodecylhydroquinone, 2-dodecylhydroquinone
, 2-dodecyl-5-chlorohydroquinone, 2-
Octyl-5-methylhydroquinone, 2-(2-octyl
tadecenyl)-5-methylhydroquinone, etc. Organic sulfur compounds dilauryl-3,3'-thiodipropionate, diste
Allyl-3,3'-thiodipropionate, ditetrade
Silu 3,3'-thiodipropionate and the like. Organophosphorus compounds triphenylphosphine, tri(nonylphenyl)phos
Phin, tri(dinonylphenyl)phosphine, tric
Resylphosphine, tri(2,4-dibutylphenoxy)
) phosphine etc. These compounds are known as antioxidants for rubber, plastics, oils and fats41-42-, and are easily available commercially.
I can do it. In the present invention, the amount of the antioxidant added is 1.
0.1 to 100 parts by weight, preferably
, 2 to 30 parts by weight. (The following is a blank space) [Example] Next, an example will be shown.
The present invention is not limited by the examples.
It's not something you can do. All parts in the examples are parts by weight.
. Example] Polyethylene terephthalate with aluminum vapor deposited
Using SnO□ powder as a starting material on a film, electron beam
A medium made of tin oxide with a thickness of 0.5 μm was created using the vapor deposition method.
An interlayer was provided. On top of this, a charge generation layer coating liquid having the following composition,
The charge transport layer coating solution was applied and dried one after another to a thickness of 0.2 μm each.
Formation of M-thick charge generation layer and 22 μm-thick charge transport layer
Then, an electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 5 parts 43- 44- Cyclohexanone 250 parts 2-
Butanone 100 parts [charge
Transport layer coating liquid] 25 parts of a charge transport substance having the following structural formula Generation layer
and a 17-tone charge transport layer, and the electrophotographic method of the present invention
A photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 4 parts tetrahydrogen
Dorofuran 200 parts Example 2 S on the target on an aluminum plate with a thickness of 0.2 mm.
Using nO2, in an atmosphere where the partial pressure ratio of argon and oxygen is ■
Then, by sputtering method, 0.3 μm thick oxidized
An intermediate layer of tin was formed. Second, the following composition
The charge generation layer coating solution and the charge transport layer coating solution are sequentially applied.
Cloth/Charge of 0.1 μm each after drying Tetrahydrofuran [Charge transport N coating liquid] 300 parts of charge transport material with the following structural formula 20 parts 45-46 (Lexan-141 manufactured by GE)
25 parts Methylene chloride 200 parts
Example 3 Sn was used as a target on electroformed nickel with a thickness of 70 mm.
The atmosphere inside the vacuum chamber has an oxygen partial pressure of 1.0 mm.
By reactive sputtering method, a film thickness of 8
A middle layer made of 00 tin oxide was formed. on this
, a charge generation layer coating solution and a charge transport layer coating solution having the following compositions:
were sequentially coated and dried to form a charge generation layer and a charge generating layer of 0.2p each.
The electrophotographic sensitivity of the present invention is
Created a light body. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 4 parts cyclohe
Xanone 2-butanone [Charge transport layer coating liquid] 200 parts 100 parts Charge transport substance having the following structural formula 20 parts Tetrahydrofuran 200 parts
Example 4 SnO is placed as a target on a nichrome plate with a thickness of 0.2 m.
Spatter is removed by introducing argon gas into the vacuum chamber.
An intermediate film made of tin oxide with a film thickness of 0.4 μm was formed by
Created a layer. Next, a charge generation layer having the following composition is formed on top of this.
Apply and dry the coating solution and charge transport layer coating solution in sequence.
each with a 0.3- and an 18-charge charge-generating layer and a charge-transporting layer.
An electrophotographic photoreceptor of the present invention was prepared. [Charge generating layer coating liquid] Charge generating substance having the following structural formula 4 parts 47- 48- cyclohexanone 150 parts Tet
Rahhydrofuran 150 parts [charge transport
Transfer layer coating liquid] Charge transport material with the following structural formula 22 parts Intermediate layer
was formed. On top of this, a charge transport layer coating solution having the following composition,
Apply charge generation layer coating solution and protective layer coating solution sequentially and dry.
each with a charge transport layer of 19 μm and a charge of 0.31 JH1.
A charge generation layer and a 2 μm protective layer are formed, and the electron
A photographic photoreceptor was created. [Charge transport layer coating liquid] Charge transport substance having the following structural formula 30 parts tetra
Hydrofuran 200 parts Example 5 As a target on an aluminum plate with a thickness of 0.5 mm.
Sn target with copper segment with surface coverage of 8%
Using a vacuum chamber, create an atmosphere with an oxygen partial pressure of 1.4 mTorr.
The film is deposited using reactive sputtering in an atmosphere.
Tetrahydrofuran made of tin oxide having a thickness of 1800A [Charge generation layer coating liquid] 220 parts of charge generation substance having the following structural formula 5 parts 49-50- Cyclohexanone Tetrahydrofuran [Protective layer coating liquid] 100 parts 250 parts Photoreceptor Created. [Charge transport layer coating liquid] 25 parts of charge transport material having the following structural formula: 90 parts of conductive titanium oxide
En 220 parts n-pig
Nol 60 parts Example 6 Targera 1- was placed on a 0.2+nm thick nickel plate.
Then, SnO□ containing 3% by weight of 5b203 was used.
sputtering by introducing argon gas into the vacuum chamber.
An intermediate layer made of tin oxide with a thickness of 1000 μm was created using the
was formed. On top of this, a charge transport layer coating solution having the following composition,
charge generation layer coating liquid, intermediate layer coating liquid and protective layer coating liquid.
Sequentially coated and dried at tA to form a charge transport layer of 20 μm each, 0
．． 2μm charge generation layer, 0.2μm intermediate layer and 5μm
Electrophotographic methylene chloride (2) of the present invention, 2-dichloroethane (charge generation layer coating liquid) 150 parts of a charge generation substance having the following structural formula 60 parts 4 parts 51-52-Toluylene-2,4 -Diisocyanate-1-0, 1 part Te1
Herahydrofuran 300 parts 4-Me
Chill-2-pentanone 50 parts [middle
Layer coating liquid] Methanol n-butanol [Protective layer coating liquid] 70 parts 40 parts Charge generation layer coating liquid and protective N coating liquid were applied and dried in sequence.
After drying, a charge transport layer of 22 μm and a charge generating layer of 0.3 μm were formed.
Forming a green layer and a protective layer of 3 parts m, electrophotography of the present invention
A photoreceptor was created. [Charge transport layer coating liquid] Charge transport substance having the following structural formula: 25 parts tin oxide
80 parts toluene
1.70 parts 2-butanone
100 copies Example 7 On an aluminum plate with a thickness of 0.3 nu, a target of S
Using n, an atmosphere with an oxygen partial pressure of 1.6 mTorr was created in the vacuum chamber.
The film was made to have a film thickness of 1 by reactive sputtering.
．． An intermediate layer made of 50OA tin oxide was prepared. this
On top, a charge transport layer coating solution having the following composition, methylene chloride [charge generation layer coating solution] 230 parts of a charge generation substance having the following structural formula 5 parts 1 to lylene-2,4-diisocyanate cyclohexane
Non 0.2 parts 150 parts 53-54-2-butanone [Protective layer coating liquid] 200 parts Methylene chloride 650 parts of a compound represented by the following structural formula 20 parts Titanium oxide 50 parts
(■) 40 parts toluene
250 parts 2-butano
70 parts Example 8 Polyethylene terephthalate having Hastelloy as a conductive layer
On the rate film, using SnO□ powder as a starting material,
Tin oxide with a thickness of 0.2 μm is made using anti-heating vacuum evaporation method.
An intermediate layer was formed. On top of this, apply a coating liquid with the following composition.
After coating and drying, a eutectic complex photosensitive layer with a dry film thickness of 15 μm was formed.
An electrophotographic photoreceptor of the present invention was prepared. (Comparative Examples 1 and 7 of Ordinary Chemical Cleavage Panlite L-1225JU) In Examples 1 and 7, no intermediate layer was provided, and
The photoreceptors of Comparative Examples 1 and 7 were prepared in the same manner as in Examples 1 and 7.
It was created. Comparative Example 2, 3.5 In Example Z, 3.5, the intermediate layer was an intermediate layer having the following composition.
The only difference was that an intermediate layer with a thickness of 0.5μ was provided instead of the coating liquid.
Photoreceptor of Comparative Example 2, 3.5 in the same manner as Example 2, 3.5
It was created. Methanol n-butanol 60 parts 40 parts Comparative Example 4 55- 56- In Example 4, the intermediate layer was coated with an intermediate layer coating solution having the following composition.
Example except that an intermediate layer with a thickness of 0.5p+n was provided instead.
A photoconductor of Comparative Example 4 was prepared in the same manner as in Comparative Example 4. SnO powder 10
Part toluylene-2,4-diisocyanate 0.1
Part 2-Butanone 100
Part Comparative Example 6 In Example 6, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Instead, an intermediate layer with a thickness of 1.07 m was provided. A photoreceptor of Comparative Example 6 was prepared in the same manner as in Example 6. SnO□ powder containing 3% of 5b2o
5 parts water
8o parts methanol
80 parts Comparative Example 8 In Example 8, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example 8 except that an intermediate layer with a thickness of 2.0 μm was provided instead.
A photoreceptor of Comparative Example 8 was prepared in the same manner as described above. SnO□ powder 20 parts water
150 parts methanol 2
The characteristics of each photoreceptor of 00 copies or more were measured using an electrostatic copying paper tester (
Using Kawaguchi Electric's new model 5P-428), do the following:
evaluated. First, -5.2KV (or +5.6KV) discharge
Pressure nite. Corona charging for 20 seconds followed by dark decay for 10 seconds.
Then, tungsten light of 10 Qux was irradiated. Surface potential v2 (V) at 2 seconds and 20 seconds after the start of charging at this time
, V2o (V) and surface potential v3n after 10 seconds of dark decay
(v) and also optically attenuate V311 to half the potential.
Exposure amount required to achieve Ell/□ (Qux-see)
was measured. In addition, the dark decay rate (D, D) is defined by the following formula
be done. D, D=V3-/Vza In addition, the surface potential after 20 seconds of the above exposure is taken as the residual potential VR.
defined. Furthermore, after electrification and exposure under the above conditions were carried out simultaneously for 30 minutes to fatigue, the same measurements as above were carried out again.
. The evaluation results are shown in Table-1. Table-1 Example 9 Polyethylene terephthalate 1~ with aluminum vapor deposited
・Electron beam processing using TiO as an evaporation material on the film
Titanium oxide with a thickness of 0.6 prn by thermal vacuum evaporation method
An intermediate layer consisting of On top of this, a charge of the following composition is generated.
The layer coating solution and the charge transport layer coating solution are applied and dried one after another.
0.2 μm thick charge generation layer and 22 μm thick charge transport layer
A layer was formed to produce an electrophotographic photoreceptor of the present invention. C charge generation layer coating liquid] Charge generation substance with the following structural formula 5 parts cyclohe
Xanone 2-butanone 200 parts 140 parts 59- 60- [Charge transport layer coating liquid] Charge transport substance having the following structural formula: 25 parts Tetrahydrofuran: 230 parts
Example 10 On an aluminum plate with a thickness of 0.2 mm, the target is T.
An atmosphere where the partial pressure ratio of argon and oxygen is 1 using iO
Below, a 0.3 μm thick layer of titanium oxide was deposited by sputtering.
An intermediate layer made of tan was provided. On top of this, add an electric current of the following composition.
Apply the charge generation layer coating liquid and the charge transport layer coating liquid in sequence.
Dry charge generation layer of 0.1 mm each and 17 charges
A transport layer was formed to produce an electrophotographic photoreceptor of the present invention. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts tetrahydrogen
Dorofuran 300 parts [charge transport layer
Coating liquid] Charge transport material with the following structural formula 30 parts Polycarbonate
carbonate (GE Lexan-141)
32 parts methylene chloride 300
Part Example Work 1 T” is applied to the target on electroformed nickel with a thickness of 70 μm.
The partial pressure ratio in the vacuum chamber is oxygen/argon = 15/85.
An intermediate layer made of titanium oxide with a thickness of 0.2 μm was formed by reactive sputtering under an atmosphere of 61 62 -. On top of this, a charge generation layer coating solution with the following composition and a charge transport layer are added.
A charge of 0.2 strokes is generated by sequentially applying and drying the layer coating solution.
Forming a biolayer and a charge transport layer of 20 layers, the electron
A photographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts cyclohe
Xanone 150 parts 2-butanone
100 parts (charge transport layer coating)
Technical fluid] Charge transport substance with the following structural formula 25 parts tetra
Hydrofuran 300 parts Example 12 Ti was used as the evaporation material on a nichrome plate with a thickness of 0.2 m.
Then, oxygen gas is introduced into the vacuum chamber and reactive ion blasting is performed.
Titanium oxide film with a film thickness of 0.25-
A middle layer was created. On top of this, a charge generation layer with the following composition is applied.
The liquid and the charge transport layer coating liquid are applied and dried one after another.
Formed with a 0.3-layer charge generation layer and an 18-layer charge transport layer.
Then, an electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] 5 parts of a charge generation substance having the following structural formula (UC,
C, m XYHL) 63- - cyclohexanone 150 parts tet
Rahhydrofuran 130 parts [charge transport
Transfer layer coating liquid] 25 parts of a charge transport substance having the following structural formula [charge
Transport layer coating liquid] 25 parts of a charge transport substance having the following structural formula, 220 parts of tetrahydrofuran.
Example 13 A target is placed on an aluminum plate with a thickness of 0.511N11.
Using Ti2O3, argon gas was introduced into the vacuum chamber.
, titanium oxide with a thickness of 0.3 mm by sputtering method.
It created a stronger middle class. On top of this, charge of the following composition
transport layer coating liquid, charge generation layer coating liquid and protective layer coating liquid.
Sequentially coated and dried to form a charge transport layer of 19p and a charge transport layer of 0.3p each.
Forming a charge generation layer of μ and a protective layer of 2, the present invention
An electrophotographic photoreceptor was created. Tetrahydrofuran [Charge generating layer coating liquid] Charge generating substance having the following structural formula 250 parts 5 parts Cyclohexanone Tetrahydrofuran 200 parts 80 parts 65-66- [Protective layer coating liquid] Conductive titanium oxide 90 parts 1-l
En 220 parts n-pig
Nol 60 parts Example 14 0.2 parts thick aluminum plate" Second, evaporate Ti.
Reactive vapor deposition using oxygen gas in a vacuum chamber
An intermediate layer made of oxygen titanium with a film thickness of 0.5 mm was created using the method.
I got it. Second, a charge transport layer coating solution with the following composition, charge
Apply generation layer coating liquid, intermediate layer coating liquid, and protective layer coating liquid in sequence.
, a charge transport layer of 20pm each after coating and drying, 0.2μ
m charge generation layer, 0.2 parts m intermediate layer and 5 parts m storage layer.
A protective layer was formed to produce an electrophotographic photoreceptor of the present invention. [Charge transport layer coating solution] 30 parts of a charge transport substance having the following structural formula
Tolylene 1,2-dichloroethane [Charge generating reverse layer coating liquid] Charge generating substance toluylene 2,4-diisocyanate tetrahydrof with the following structural formula
Ran 4-methyl-2-pentanone [Intermediate layer coating liquid] Alcohol-soluble polyamide 180 parts 80 parts 0.2 parts 100 parts 1.50 parts-6 (Amiran CM-8000 manufactured by Toshi ■) Methanol 70 parts n-butyl
Tanol 40 parts [protective layer
Coating liquid] 25 parts of charge transporting substance with the following structural formula: 80 parts of tin oxide
en 1.70 parts 2-
Butanone 100 parts example
15 TiO is placed as a target on a nickel plate with a thickness of 0.3 mr.
In an atmosphere where the partial pressure ratio of argon and oxygen is 1,
Titanium oxide film with a thickness of 0.77 ann was created using the sputtering method.
An intermediate layer was formed. On top of this, charge of the following composition
transport layer coating liquid, charge generation layer coating liquid and protective layer coating liquid.
A charge transport layer of 22 μm and a charge transport layer of 0.0 μm were sequentially coated and dried.
A charge generation layer of 3 μm and a protective layer of 3 μm were formed.
An electrophotographic photoreceptor of the invention was created. [Charge transport layer coating liquid] Methylene chloride [Charge generation layer coating liquid] Charge generation substance 1 of the following structural formula - Louisene-2,4 - diisocyanate cyglohexa
Non-2-butanone [protective layer coating liquid] 250 parts 0, 1 part 180 parts 85 parts 69- 70- Tin (II) oxide 40 parts
Toluene 250 parts 2
-Butanone 70 parts comparative example
9,15 In Examples 9 and 15, no intermediate layer was provided, respectively.
The rest was the same as in Examples 9 and 15, and in Comparative Examples 9 and 15.
A photoreceptor was created. Methanol 60 parts n-bu
Tanol 40 parts Comparative example 1
0 In Example 10, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 0.5 μm was provided instead of
A photoreceptor of Comparative Example 10 was prepared in the same manner as Comparative Example 10. TiO□ powder 10 parts
Luylene-2,4-diisocyanate 0.1 part 2
-Butanone 100 parts ratio
Comparative Example 1 In place of the intermediate layer made of titanium oxide in Example 1
Using an intermediate layer coating liquid with the following composition, a thickness of 1.0/Im was applied.
Comparative Example 1 was prepared in the same manner as in Example 11 except that an intermediate layer was provided.
Photoconductor No. 1 was prepared. Ti2O3 powder 5 parts water
　　　　　　　　　　　　　　　　　　　　　　　　　
80 parts methanol 80 parts
Comparative Example 12.13 In Example 12.13, no intermediate layer was provided, respectively.
Other than that, Comparative Example 12.
Thirteen photoreceptors were prepared. Comparative Example 14 In Example 14, instead of the intermediate layer made of titanium oxide
Using an intermediate layer coating liquid with the following composition,
Comparative Example 14 was prepared in the same manner as Example 14 except that an interlayer was provided.
A photoreceptor was created. 71- 72- Toluene 20 parts or more
The characteristics of each photoreceptor were measured using an electrostatic copying paper tester (manufactured by Kawaguchi Electric).
The evaluation was made as follows using a newly manufactured model 5P-428). First, -5.2KV (or +5.6KV) (7)
Perform discharge pressure and corona charging for 20 seconds, then 1
Dark decay for 0 seconds, then 1 (lQux of tungsten
irradiated with light. At this time, the surface potential Vi (v
), V2. (V) and surface potential V3 after 10 seconds of dark decay
0 (V) and also optically attenuate v3o to half the potential.
The exposure amount required to
was measured. In addition, the dark decay rate (D, D) is defined by the following formula
be done. D, D=V3. /V. In addition, the surface potential after 20 seconds of the above exposure is defined as the residual potential vR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-2. Table 2 73- 74- Example 17 Polyethylene terephthalate with aluminum vapor deposited
Using In2O3 as a target on the film, inside a vacuum chamber
by sputtering method by introducing argon gas into
An intermediate layer made of indium oxide with a thickness of 0.3 IJm was set up.
I got it. On top of this, a charge generation layer coating liquid with the following composition, charge transport
The layer coating solution was applied and dried one after another to form an electrode with a thickness of 0.2 μm.
A charge generation layer and a charge transport layer with a thickness of 22 μm were formed, and the present invention
A bright electrophotographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
300 parts of xanone 2-butanone 100 parts [Charge transport M refrigeration fluid] 25 parts of charge transport substance with the following structural formula Tetrahydrofuran 200 parts
Example 18 A tartar was placed on an aluminum plate 1- with a thickness of 0.2III111.
In2 containing 5% by weight of SnO2 in galley 1~1~
Introduce argon gas into the vacuum chamber using O.
Indium oxide with a film thickness of 0.2 pa was made by the uttering method.
An intermediate layer was formed. On top of this, charge of the following composition
Apply and dry the generation layer coating solution and charge transport layer coating solution in sequence.
After drying, a charge generating layer of O, ]μ and a charge generating layer of 17 μm were formed.
A cargo transport layer was formed to produce an electrophotographic photoreceptor of the present invention.
. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 5 parts 5 6- 2 parts of polyester [Charge transport layer coating liquid] Charge transporting substance having the following structural formula 25 parts film thickness
An intermediate layer made of indium oxide with a thickness of 0.15 μm was provided.
. On top of this, a charge generation layer coating solution with the following composition and a charge transport layer are added.
The layer coating solution was applied and dried in sequence to form a coating of 0.2 parts and 7 m each.
A charge generation layer and a charge transport layer of 20 μm were formed, and the present invention
A bright electrophotographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts methyl chloride
Len 200 parts Example 19 In is placed on the target on electroformed nickel with a thickness of 70 mm.
An atmosphere with an oxygen partial pressure of 1.5 millitorr is used in the vacuum chamber.
The reactive sputtering method cyclohexano
2-butanone [Charge transport layer coating liquid] Charge transport material having the following structural formula: 100 parts 100 parts 30 parts - 77 = 78- Example 20 On a nichrome plate with a thickness of 0.2 + nm, In2O3 and In
The starting material is a mixture of
electron beam evaporation method (reactive
Made of indium oxide with a thickness of 0.8 μm by vapor deposition method)
A middle layer was created. On top of this, apply a charge generation layer with the following composition.
The coating solution and the charge transport layer coating solution are applied and dried one after another.
0.3 μm charge generation layer and 18 parts m charge transport layer
An electrophotographic photoreceptor of the present invention was prepared by applying the method. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts cyclohe
Xanone Tetrahydrofuran 150 parts 200 parts [Charge transport layer coating liquid] 27 parts of charge transport substance having the following structural formula Tetrahydrofuran 350 parts
Example 21 Polyethylene terephthalate with nickel as a conductive layer
On the base film, using In2O3 as a target,
Sputtering in an atmosphere where the partial pressure ratio of Rougon and oxygen is 1.
From indium oxide with a film thickness of 0.1μ by the ring method.
An intermediate layer was formed. On top of this, apply a coating liquid with the following composition.
Coating and drying to form a eutectic complex photosensitive layer with a dry film thickness of 15 mm.
Thus, an electrophotographic photoreceptor of the present invention was prepared. Methylene chloride 650 parts The following composition
20 parts of the compound represented by the following structural formula
30 parts of charge transport material h3 Example 22 A target was placed on an aluminum plate with a thickness of 0.2+nm.
Using In, the oxygen partial pressure in the vacuum chamber is 1.0 mTorr.
using reactive sputtering method under an atmosphere of
An intermediate layer made of indium oxide with a thickness of 0.1 μm is provided.
Ta. On top of this, a charge transport layer coating solution with the following composition, a charge generation
The layer coating solution and the protective layer coating solution are applied and dried one after another.
19 charge transport layers, 0.3 charge generation layers, and
The electrophotographic photoreceptor of the present invention is prepared by forming a protective layer of 2 parts.
accomplished. [Charge transport layer coating solution] Tetrahydrofuran [Charge generation layer coating solution] 300 parts of charge generating substance with the following structural formula 3 parts cyclohexanone tetrahydrofuran [Protective layer coating solution] 200 parts 80 parts 81- 82- Conductivity Titanium oxide 90 parts 1 health
En 220 parts n-pig
Nol 60 parts Example 23 In2O3 powder was poured onto a 0.2wn thick nickel plate.
As a starting material, the thickness is 0.5 mm using the vacuum evaporation method using the resistance heating method.
An intermediate layer of indium oxide of .mu.m was formed. this
On top, a charge transport layer coating liquid and a charge generation layer coating liquid having the following compositions.
and protective layer coating solution were sequentially applied and dried, and each
μm charge transport layer, 0.2μm charge generation layer, 0.2μm
The electrode of the present invention has an intermediate layer of 5 μm and a protective layer of 5 μm.
A child photographic photoreceptor was created. [Charge transport layer coating liquid] 25 parts of a charge transport substance having the following structural formula
Tolylene 1,2-dichloroethane [Charge generation layer coating liquid] Charge generation substance toluylene-2,4-diisocyaki 1-tetrahydro having the following structural formula
Furan 4-methyl-2-pentanone [intermediate layer coating liquid] ioo part 100 parts 0.1 part 100 parts 200 parts (Polycarboy manufactured by Mitsubishi Bonsikaji ■, -hZ) Methanol n-butanol 70 parts 40 parts 3- [Protective layer coating liquid] Tin oxide 80 parts Toluene
170 parts 2-butano
100 copies Example 24 Targera 1- and 0.3 mm thick aluminum plate
and has aluminum segments with a surface coverage of 8%.
Using an In target, the oxygen partial pressure in the vacuum chamber is 1.0.
Reactive spatter in an atmosphere of millitorr
Made of indium oxide with a film thickness of 0.15 μm using the
An interlayer was provided. On top of this, apply a charge transport layer coating solution with the following composition.
, charge generation layer coating liquid and protective N coating liquid were applied in sequence.
Dry to 22μM each charge transport layer, 0.3μM charge
A generation layer and a protective layer of 3 μm are formed, and the electrophotography of the present invention is
A euphotoreceptor was created. [Charge generation layer coating liquid] 30 parts of a compound represented by the following structural formula
Tyrene [Charge generation layer coating liquid] Compound 1-lylene-2,4-diisocyanate cyclohexane represented by the following structural formula
Non-2-butanone [Protective M coating liquid] 300 parts 0.2 parts 200 parts 150 parts 5- 86- Tin oxide (n) 40 parts
Ruen 250 parts 2-
Butanone 70 parts Comparative Example 1
7.22 In Example 17.22, no intermediate layer was provided, respectively.
Other than that, Comparative Example 17.
22 photoreceptors were prepared. Comparative Example 18 In Example 18, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example 1 except that an intermediate layer with a thickness of 0.5 nm was provided instead of
A photoreceptor of Comparative Example 18 was prepared in the same manner as in Example 8. In2O3 powder containing 5wt% SnO2
10 parts toluylene-2,4-diisocyanate
0.1 part 2-butanone
100 parts Comparative Examples 19, 23.24 In Examples 19, 23.24, the intermediate layer had the following composition.
In addition to providing an intermediate layer with a thickness of 0.3 - in place of the intermediate layer coating liquid.
Comparative Example 19° was prepared in the same manner as Examples 19, 23, and 24.
No. 23 and 24 photoreceptors were prepared. Methanol 60 parts n-bu
Tanol 40 parts Comparative example 2
0 In Example 20, the intermediate layer made of indium oxide
Instead, use an intermediate layer coating liquid with the following composition, and the thickness is 1.0 μm.
A comparative example was prepared in the same manner as in Example 20 except that an intermediate layer was provided.
Twenty photoreceptors were prepared. In2O3 powder 5 parts water
　　　　　　　　　　　　　　　　　　　　　　　　　
80 parts methanol 80 parts
Comparative Example 2 In Example 21, the intermediate layer made of indium oxide
Instead, use an intermediate layer coating liquid with the following composition, and apply a coating with a thickness of 2.0 units.
Comparative Example 2 was carried out in the same manner as in Example 21 except that an intermediate layer was provided.
Photoconductor No. 1 was prepared. 87-88 In2O3 powder 20 parts Toluene 20 parts or more
The characteristics of each photoreceptor were measured using an electrostatic copying paper tester (manufactured by Kawaguchi Electric).
The evaluation was made as follows using a newly manufactured model 5P-428). First, -5.2KV (or +5.6KV) discharge
Apply pressure and corona charging for 20 seconds, then 10 seconds.
After dark decay, tungsten light of 10 flux was irradiated.
I shot it. At this time, the surface potential VX (V
), V2o (V) and surface potential V3 after 10 seconds of dark decay
．． (V) and also optically attenuate Van to half the potential.
Exposure amount E□/2 (Qux-sec) required to
was measured. In addition, the dark decay rate (D, D) is defined by the following formula
be done. D, D=V3°c. In addition, the surface potential after 20 seconds of the above exposure is defined as the residual potential vR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-3. Table 3 9 90- Example 25 Polyethylene terephthalate with aluminum vapor deposited
Resistance heating method using Fe2O3 as the vapor deposition material on the film
A medium made of iron oxide with a thickness of 1.0p was made using the vacuum evaporation method of
An interlayer was provided. On top of this, apply a charge generation layer coating solution with the following composition.
, charge transport layer coating solution was sequentially applied and dried to give a coating solution of 0.2
Part 1 m thick charge generation layer and 22 parts m thick charge transport layer.
An electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
Xanone 2-butanone 300 parts 50 parts [Charge transport layer coating liquid] 30 parts of charge transport substance having the following structural formula Tetrahydrofuran 260 parts
Example 26 Fe is used as the evaporation material on an aluminum plate with a thickness of 0.2 mm.
0□ gas is introduced into the vacuum chamber using a reactive vapor deposition method.
An intermediate layer made of iron oxide with a thickness of 0.7 mm was provided. child
On top of this, a charge generation layer coating solution and a charge transport layer having the following composition are applied.
Apply and dry the coating solution in sequence to generate a charge of 0.1 μm each.
Form a charge transport layer of raw N and 17μ of the charge transport layer of the present invention.
A child photographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 5 parts 91-2 Polyester (Vylon 300 manufactured by Toyobo ■) Tetrahydrofuran [Charge transport layer coating liquid] Charge transport substance having the following structural formula 1 part 300 parts 25 300 parts methylene chloride
Example 27 On electroformed nickel with a thickness of 70 mm, the target is Fe2
Using O3, the partial pressure ratio of argon and oxygen gas is 1.
Sputtering method under atmosphere to a thickness of 0.4 ton of acid
An intermediate layer made of iron chloride was provided. This upper layer has the following composition.
Sequentially apply charge generation layer coating solution and charge transport M coating solution
-Dried charge generating layer of 0.2 μm each and 20 parts m
A charge transport layer is formed to produce an electrophotographic photoreceptor of the present invention.
did. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts cyclohe
Xanone 2-butanone [Charge transport layer coating liquid] Charge transport substance having the following structural formula: 100 parts 160 parts 25 parts Tetrahydrofuran 280 parts
Example 28 Fe is added to the evaporation material on a nichrome plate with a thickness of 0.2 nn.
Using Taiichi, oxygen gas is introduced into the vacuum chamber to perform reactive ion blasting.
An intermediate film made of iron oxide with a thickness of 0.31 m was created using the tinging method.
formed a layer. On top of this, apply a charge generation layer coating solution with the following composition.
and charge transport layer coating solution were sequentially applied and dried to 0.
．． Formed 3 charge generation layers and 18/Im charge transport layer.
An electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] Trigonal selenium 10 parts Polyvinyl
Nylcarbazole 10 parts 2-butanone
60 parts toluene
60 parts [Charge transport layer coating liquid
] Charge transport substance with the following structural formula 30 parts tetra
Hydrofuran 280 parts Example 29 On an aluminum plate with a thickness of 0.5 mm, Fe was added as an evaporation material.
Using 2O3, the vacuum evaporation method uses electron beam heating.
An intermediate layer made of iron oxide with a thickness of 0.9 μm was formed. In addition to this, the charge transport W! of the following composition is added! J coating liquid, charge generation
Apply and dry the layer coating liquid and protective layer coating liquid in sequence,
Each has a charge transport layer of 19 layers, a charge generation layer of 0.3μ and
Two protective layers were formed to produce the electrophotographic photoreceptor of the present invention.
did. [Charge transport layer coating liquid] 25 parts of a charge transport substance having the following structural formula (Uni
Tetrahydrofuran 280 parts (manufactured by Chika U-100)
Charge-generating layer coating liquid] Charge-generating substance with the following structural formula 3 parts 95-96- cyclohexalantetrahydrofuran [Protective layer coating liquid] 150 parts 100 parts Cloth/Charge transport layer of 20p each after drying, 0.2- charge of
Forms generation layer, 0.2 μm intermediate layer and 5 protective layers
Then, an electrophotographic photoreceptor of the present invention was prepared. [Charge transport layer coating liquid] Charge transport material with the following structural formula 30 parts Conductive
Titanium oxide 90 parts toluene
220 parts n-butanol
60 parts Example 30 Fe was placed on a 0.2 mm thick nickel plate as an evaporation material.
Using 3O4, a film thickness of 1.3 mm was obtained using a resistance heating vacuum evaporation method.
An intermediate layer of 2 μm of iron oxide was formed. On top of this
Charge transport layer, charge generation layer coating liquid, and intermediate layer coating with the following compositions:
The solution and the protective layer coating solution were sequentially coated: methylene chloride 1,2-dichloroethane [charge generation layer coating solution] 200 parts of a charge generation substance having the following structural formula: 60 parts 5 parts 98% tetrahydrofuran 4-methyl-2-pentanone [intermediate] Layer coating solution] 200 parts 50 parts methanol n-butanol [Protective layer coating solution] 70 parts 40 parts A charge transport layer of 0.22 μm and a protective layer of 0.022 μm were formed and created. [Charge Transport Layer Coating Solution] A 0.3 μm charge generation layer containing a charge transport material having the following structural formula and the electrophotographic photoreceptor of the present invention, 25 parts tin oxide, 80 parts toluene.
170 parts 2-pig
Non 100 copies Example 3
1 Aluminum plate with a thickness of 0.3 mm
Using Fe3O4, the partial pressure ratio of argon and oxygen gas is ■.
A film thickness of 0.3 μm was obtained by sputtering under an atmosphere of
An intermediate layer made of iron oxide was created. Second, below
Composition of charge transport N coating liquid, charge generation layer coating liquid and protection
The layer coating liquids were sequentially coated and dried, and each methylene chloride [charge generation layer coating liquid] 250 parts of a charge generating substance having the following structural formula: 5 parts, 9 parts, 100 1-lylene-2,4-diisocyane-1-0, 2nd part
Clohexanone] 7770 parts 2
-Butanone 100 parts [protective layer
Coating liquid] Methylene chloride 650 parts or less
Compound represented by the structural formula 20 parts titanium oxide
50 parts tin oxide (U)
40 parts toluene
250 parts 2-butanone
70 parts Example 32 Polyethylene terephthalate having Hastelloy as a conductive layer
Second, using Fe2O3 as the target
, sputtering method using argon gas introduced into the vacuum chamber
An intermediate layer made of iron oxide with a thickness of 0.3 μm was created by
I got it. On top of this, apply a coating liquid with the following composition and dry it.
A eutectic complex photosensitive layer with a dry film thickness of 15 μm was provided, and the electron
A photographic photoreceptor was created. Comparative Example 25.31 In each of Example 25.31, no intermediate layer was provided.
Comparative Example 25. was prepared in the same manner as Example 25.31 except for the above.
31 photoreceptors were prepared. Comparative Examples 26, 27.29 In Examples 2G and 27.29, the intermediate layer had the following composition.
Instead of the intermediate layer coating liquid, an intermediate layer with a thickness of 0.3 IJm is provided.
Other than that, Comparative Example 2 was carried out in the same manner as in Examples 26, 27, and 29.
A photoreceptor having a diameter of 6°27.29 was prepared. 150 parts of water and methanol 200 parts - 101 - 102 - Comparative Example 28 In Example 28, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example 2 except that an intermediate layer with a thickness of 0.5 μm was provided instead.
A photoreceptor of Comparative Example 28 was prepared in the same manner as in Example 8. Fe2O3 powder 10 parts
In Example 32, the intermediate layer made of iron oxide had the following composition.
Instead of the intermediate layer coating liquid, an intermediate layer with a thickness of 2.0p+n is provided.
Other than that, the photoreceptor of Comparative Example 32 was prepared in the same manner as in Example 32.
Created. 20 parts of Fe2O3 powder
Luylene-2,4-diisocyanate 0.1 part 2
-Butanone 100 parts comparison
Example 30 In Example 30, the intermediate layer made of iron oxide had the following composition.
In place of the intermediate layer coating liquid, an intermediate layer with a thickness of 1.0 pm is provided.
Other than that, the photoreceptor of Comparative Example 30 was prepared in the same manner as in Example 30.
Created. Fe2O3 powder 5 parts Water Methanol 80 parts 80 parts Comparative Example 32 Toluene 20 parts or more
The characteristics of each photoreceptor were measured using an electrostatic copying paper tester (manufactured by Kawaguchi Electric).
The evaluation was made as follows using a newly manufactured model 5P-428). First, -5.2KV (or +5.6KV) (7)
Perform discharge pressure and corona charging for 20 seconds, then 1
Dark decay for 0 seconds, then 10 flux tungsten
irradiated with light. Surface potential V2 (V) at 2 seconds and 15 seconds after the start of charging at this time
, v, 5 (V) and surface potential v2 after 10 seconds of dark decay
5(v) and also v2. , the light decreases to half the potential
Measure the exposure amount E□/2 (Qux-see) required to attenuate 103-104-
Ta. Note that the dark decay rate (D, D) is defined by the following equation. D, D=v25/v□5 Also, the surface potential after 20 seconds of the above exposure is taken as the residual potential vR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table 4. Table 4 -105- -106- Example 33 Polyethylene terephthalate L/-t with aluminum vapor deposited
・Electrons are formed on the film using 1, a2o3 powder as a starting material.
From lanthanum oxide with a thickness of 0.7 μm by beam evaporation method
An intermediate layer was formed. On top of this is a charge generation layer with the following composition.
Coating liquid and charge transport layer coating liquid are applied and dried one after another.
A 0.2 μm thick charge layer and a 22 μm thick charge transport layer.
An electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] 5 parts of a charge transporting substance having the following structural formula QCQ 200 parts of cyclohexanone 2-butanone 100 parts [Charge transporting layer coating liquid] 25 parts of a charge transporting substance having the following structural formula 300 parts of TeI-lahitorofuran
Example 34 Targera 1-L on an aluminum plate with a thickness of 0 and 2 mm
a,,0. 5 to 20 millimeters of 1 to
Introduce argon gas and use sputtering method to thicken the film.
An intermediate layer of 0.5 pm lanthanum oxide was formed.
. On top of this, a charge generation layer coating solution with the following composition and a charge transport layer are added.
The layer coating solution was applied and dried one after another to form a 0.1μm electric current.
A charge generation layer and a charge transport layer of the present invention are formed.
An electrophotographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 4 parts-107
~ 08 Tetrahydrofuran 280 parts
Charge transport layer coating liquid] 28 parts charge transport material with the following structural formula
A charge of 0.2 μm is generated by sequentially applying and drying the solution.
layer and 20 parts m of the charge transport layer to form an electron transport layer of the present invention.
A photographic photoreceptor was created. [Charge-generating M coating liquid] Charge-generating substance with the following structural formula: 3 parts methoxychloride
260 parts Example 35 On electroformed nickel with a thickness of 70 mm, La2 was applied to Targera I-.
0. , and create an atmosphere where the partial pressure ratio of argon and oxygen is 1.
An acid film with a thickness of 0.4 μm was applied by sputtering under atmospheric pressure.
An intermediate layer of lanthanum chloride was provided. On top of this, the following group
Coating liquid for charge generation layer and charge layer cyclohexanone 2-butanone [Coating liquid for charge transport layer] 200 parts of charge transport substance having the following structural formula: 70 parts, 30 parts - 110 parts - Tetrahydrofuran: 300 parts
Example 36 La is applied as a target on a nichrome plate with a thickness of 0.2 mm.
An atmosphere with an oxygen partial pressure of 10 to 20 mTorr is created in the vacuum chamber.
By reactive sputtering method in an atmosphere,
An intermediate layer made of lanthanum oxide with a film thickness of 0.25 IJm was set up.
I got it. On top of this, a charge generation layer coating solution of the following composition and a charge generation layer coating solution of the following composition are added.
Cargo transportation N coating liquid was applied and dried one after another, and each
A charge generation layer and an 18-charge transport layer are formed, and the present invention
An electrophotographic photoreceptor was prepared. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
200 parts of xanone Tetrahydrofuran [Charge transport layer coating liquid] 90 parts of a charge transport substance having the following structural formula 25 parts Tetrahydrofuran 300 parts
Example 37 A target is placed on an aluminum plate with a thickness of 0.5+m+.
Using La, the oxygen partial pressure inside the vacuum chamber is 20 to 40 mTorr.
For the reactive sputtering method,
Therefore, an intermediate layer made of lanthanum oxide with a film thickness of 0.4 μm is formed.
Established. On top of this, apply a charge transport layer coating solution with the following composition, charge
Apply and dry the generation layer coating liquid and protective layer coating liquid in sequence.
and a charge transport layer of 19/1 m and a charge generation of 0.31 A, respectively.
The electrophotographic image of the present invention is formed by forming a green layer and a protective layer of 2 μm.
A photoreceptor was created. [Charge transport layer coating liquid] -111- -112- 30 parts of a charge transport substance having the following structural formula Tetrahydrofuran [Charge generating layer coating liquid] 280 parts of a charge generating substance having the following structural formula 4 parts Cyclohexanone Tetrahydrofuran [Protective layer coating Liquid] 170 parts 110 parts Rate copolymer conductive titanium oxide 90 parts Toluene
220 parts n-butano
60 parts Example 38 On a nickel plate with a thickness of 0.2 mm, the same plate as in Example 34 was
Thickness 0.2. An intermediate layer made of lanthanum oxide is provided.
Ta. On top of this, a charge transport layer coating solution with the following composition, a charge generation
Apply the layer coating solution, intermediate layer coating solution, and protective layer coating solution in sequence.
Cloth/Dry charge transport layer of 20μm each, 0.2-μm charge transport layer
Load generation layer, o, 2. form the intermediate layer of m and the protective layer of 5
An electrophotographic photoreceptor of the present invention was prepared. [Charge transport layer coating liquid] Charge transport material with the following structural formula: 26 parts chloride
200 parts of tyrene 1,2-dichloroethane 70 parts -113- -114- [Charge generation layer coating liquid] 5 parts of charge generation substance having the following structural formula Toluylene-2,4-cyisocyakitotetrahytotroph
Ran 4-methyl-2-pentanone [Intermediate Ra coating liquid] 0.2 parts 200 parts 80 parts 1 - Luene 170 parts 2
-Butanone 100 copies carried out
Example 39 Same as Example 35 on an aluminum plate with a thickness of 0.3 mm.
An intermediate layer of lanthanum oxide with a thickness of 0.6 pm was prepared in the same way.
Layers were set up. On top of this, a charge transport layer coating solution having the following composition,
Apply and dry the charge generation layer coating liquid and the protective layer coating liquid in sequence.
After drying, a charge transport layer of 227ym each and a charge of 0.3pIQ were formed.
The electron beam of the present invention is formed by forming a charge generation layer and a 3 μm protective layer.
A photographic photoreceptor was created. [Charge transport layer coating liquid] Charge transport substance having the following structural formula: 25 parts methano
n-butanol [Coating liquid for protective layer] 70 parts 40 parts Tin oxide 80 parts Methylene chloride [Coating liquid for charge generation layer] Charge generating substance with the following structural formula 280 parts 5 parts 15 16 Titanyl phthalocyanine 1 Helylene-2, 4-Sicyclohexanone 2-butanone [Protective layer coating liquid] Socyane-1-0,1 parts 150 parts 110 parts Methylene chloride 650 parts The following structure
Compound represented by the formula 20 parts titanium oxide
50 parts tin(II) oxide
40 parts 1-Luene
250 parts 2-butanone
70 parts Example 40 Polyethylene terephthalate having Hastelloy as a conductive layer
A film thickness of 1 was applied to the film using the same method as in Example 33.
An intermediate layer of lanthanum oxide of μm was formed. this"
Second, apply a coating liquid with the following composition and dry it, with a dry film thickness of 15
The electrophotographic photoreceptor of the present invention is provided with a photosensitive layer similar to that of IM.
It was created. Comparative Example 33.39 In each of Examples 33.39, no intermediate layer was provided.
Other than that, Comparative Example 33.
Thirty-nine photoreceptors were prepared. Comparative Examples 34, 35.37 In Examples 34, 35.37, the intermediate layer had the following composition.
Instead of the intermediate M coating liquid, an intermediate layer with a thickness of 0.37 parts m was provided.
Other than that, Comparative Example 3 was prepared in the same manner as in Examples 34, 35, and 37.
A photoreceptor having a diameter of 4°35.37 was prepared. 50 parts of water-soluble polyvinyl butyral 117
- 118 water
150 parts methanol
200 parts Comparative Example 36 In Example 36, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 0.5 μm was provided instead of
A photoreceptor of Comparative Example 36 was prepared in the same manner as Comparative Example 36. 10 parts of La2O3 powder (
Denka Poval H-20) water manufactured by Denki Kagaku Kogyo ■
80 copies
Tanol 80 parts Comparative Example 4
0 In Example 40, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 2.0 pm was provided instead of
A photoconductor of Comparative Example 40 was prepared in the same manner as Comparative Example 40. La2O3 powder 20 parts
Toluylene-2,4-diisocyanate 0.1 part 2-butylene
Tanon 100 copies comparative example
38 In Example 38, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 1.0 μm was provided instead of
A photoreceptor of Comparative Example 38 was prepared in the same manner as Comparative Example 38. La2O3 powder 5 parts
Rivinyl alcohol 2 parts Toluene
20 copies or more of each exposure
The properties of the body were measured using an electrostatic copying paper tester (newly manufactured by Kawaguchi Electric 5).
P-428 type) was used for evaluation as follows. First, -5.2KV (or +5.6KV) discharge
Apply pressure, corona charge for 20 seconds, then 10 seconds.
After dark decay, tungsten light of 10 flux was irradiated.
I shot it. Surface potential V2 (V) at 2 seconds and 15 seconds after the start of charging at this time
, v15(v) and surface potential V2S after 10 seconds of dark decay
(V) and also optically attenuate V25 to half the potential.
Measure the exposure amount E1/□ (Qux-sec) required to
Established. Note that the dark decay rate (D, D) is defined by the following formula:
Ru. D, D''V25/Vls In addition, the surface potential after 20 seconds of the above exposure is taken as the residual potential vR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-5. Table-5 -121- -122- Example 41 Polyethylene terephthalate with aluminum vapor deposited
Argon and acid were applied to the film using ZnO as a target.
The sputtering method is used in an atmosphere where the partial pressure ratio of the element is 1.
An intermediate layer made of zinc oxide with a thickness of 0.5 μm was provided. On top of this, coat a charge generation layer coating solution and a charge transport layer with the following composition.
Apply and dry the liquid one after another to generate a charge with a thickness of 0.2 μm each.
layer and a 220 part thick zero charge transport layer to form a charge transport layer of the present invention.
A child photographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
Xanone 2-butanone 200 parts 1.00 parts [Charge transport layer coating liquid] 26 parts of charge transport substance having the following structural formula Tetrahydrofuran 250 parts
Example 42 Zn is evaporated on an aluminum plate with a thickness of 0.2 mm
Using a reactive ion bulb, oxygen gas is introduced into the vacuum chamber.
From zinc oxide with a film thickness of 0.3 μm using the rating method.
A middle layer was created. On top of this, a charge generation layer with the following composition
Apply and dry the coating solution and charge transport layer coating solution in sequence.
0.1 part m of each charge generation layer and 17p111 charge
A transport layer was formed to produce an electrophotographic photoreceptor of the present invention. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 4 parts - 123
- 124 Tetrahydrofuran [Charge Transport Layer Coating Solution] An intermediate layer consisting of 120 parts, 25 parts, and 0.4 μm of zinc oxide of a charge transport material having the following structural formula was provided. above this
A charge generation layer coating solution and a charge transport M coating having the following composition were applied.
The liquid was applied and dried one after another to form a charge generation layer of 0.2 μm each.
and 20 to form a charge transport layer of the electrophotographic method of the present invention.
A photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts methyl chloride
Len 200 copies Example 43 Using ZnO as a target on electroformed nickel with a thickness of 70 units
The partial pressure ratio of argon and oxygen is Ar102 = 8/2.
The film thickness was increased by sputtering in an atmosphere of
Sanon 2-butanone [Charge transport layer coating liquid] 100 parts of charge transport substance with the following structural formula 200 parts 30 parts - 126 - Tetrahydrofuran 250 parts
Example 44 Zn (C21(s)
)2 and 0□ raw material gases are introduced while being diluted with Ar,
Made of zinc oxide with a film thickness of 0.7 μm by CVD method
It gave shape to the interlayer. On top of this, apply a charge generation layer with the following composition.
The liquid and the charge transport layer coating liquid are applied and dried one after another.
Formed 0.3μm charge generation layer and 18μm charge transport layer.
Then, an electrophotographic photoreceptor of the present invention was prepared. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
230 parts of xanone tetrahydrofuran 80 parts [Charge transport layer coating liquid] 25 parts of charge transport substance having the following structural formula Tetrahydrofuran 220 parts
Example 45 A Zn target was placed on an aluminum plate with a thickness of 0.5 m.
Sputter using O and introducing argon gas into the vacuum chamber.
Made of zinc oxide with a film thickness of 0.3p by the taring method.
Created an interlayer. On top of this, a charge transport layer with the following composition is applied.
Apply liquid, charge generation layer coating liquid, and protective layer coating liquid in sequence.
・Dry, 19 yen each. charge transport layer, 0.3 pm charge generation layer and two
A protective layer was formed to prepare an electrophotographic photoreceptor of the present invention. [Charge transport layer coating liquid] Charge transport substance having the following structural formula 25 parts-12
7- Tetrahydrofuran [Charge generation layer coating solution] 250 parts of charge generation substance with the following structural formula 5 parts Cyclohexanone Tetrahydrofuran [Protective layer coating solution] 200 parts 100 parts Conductive titanium oxide 90 parts Toluene
220 parts n-butano
60 parts Example 46 Same as Example 42 on a 0.2 nyn thick nickel plate.
An intermediate layer made of zinc oxide with a film thickness of 0.2/#11 is formed using the method.
Established. On top of this, apply a charge transport layer coating solution with the following composition, charge
Apply generation layer coating liquid, intermediate layer coating liquid, and protective layer coating liquid in sequence.
, coated and dried to form 20 charge transport layers and 0.2 layers each.
Charge generation layer, 0.2 μm intermediate layer and 5 μm protective layer
An electrophotographic photoreceptor of the present invention was prepared by applying the method. [Charge transport layer coating liquid] Charge transport substance having the following structural formula 30 parts-13
0- Methylene chloride 1,2-dichloroethane [Charge generation layer coating liquid] Charge generation substance toluylene-2,4-diisosiapho-1-tetrahydro having the following structural formula
Furan 4-methyl-2-pentanone [intermediate layer coating liquid] Methanol n-butanol [protective layer coating liquid] Styrene-methyl methacrylate-h 150 parts 100 parts 5 parts 0.2 parts 150 parts 150 parts Tin oxide 80 Department Trouet
1.70 parts 2-bu
Tanon 400 copies Example 4
7 Zn (C5H□
0. ) 2 and 1 (20 are used as raw material gas system, in a vacuum chamber
oxidized to a film thickness of 0.4 μm by CVD method while introducing
An intermediate layer of zinc was provided. On top of this, add an electric current of the following composition.
Load transport layer coating liquid, charge generation layer coating liquid, and protective layer coating liquid
were sequentially coated and dried to form a charge transport layer of 22 pm each,
Forming a charge generation layer of 0.3μ and a protective layer of 3m,
An electrophotographic photoreceptor of the present invention was prepared. [Charge transport layer coating liquid] Charge transport substance having the following structural formula 25 parts 70 parts 40 parts 80 parts (Hunter 1 diacid cleavage panlite C-1400)] 31 32- Methylene chloride [Charge generation layer coating liquid] Below Structural formula of charge generating substance toluylene-2,4-diisocyaphor 1-cyclohexane
Non-2-butanone [Protective layer coating liquid] Titanium oxide tin (II) oxide Toluene 2-butanone Comparative example 41.47 Example 41. ．． Comparative Example 4 was prepared in the same manner as in Example 41.47, except that 280 parts, 4 parts, 0.2 parts, 180 parts, 120 parts, 50 parts, 40 parts, 250 parts, and 70 parts were used.
A photoreceptor of 1.47 was prepared. Comparative Example 42 In Example 42, the intermediate layer made of zinc oxide was prepared using the following combination.
Instead of using the same intermediate layer coating liquid, we created an intermediate layer with a thickness of 2.0 mm.
Other than that, the photoconductor of Comparative Example 42 was prepared in the same manner as in Example 42.
Created. ZnO powder 20 parts
Toluene 20 parts comparison
Example 43.46 In Example 43.46, the intermediate layer has the following composition:
In place of the coating liquid, an intermediate layer with a thickness of 0.3 meters was provided.
Exposure of Comparative Example 43.46 in the same manner as Example 43.46
created a body. No intermediate layer provided -133- 134- Methanol 60 parts n-bu
Tanol 40 parts Comparative example 4
4 In Example 44, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example 4 except that an intermediate layer with a thickness of 0.5 mm was provided instead of
A photoreceptor of Comparative Example 44 was prepared in the same manner as in Example 4. ZnO powder 10 parts
Toluylene-2,4-diisocyane-1 to 0.1
Part 2-Butanone 100 parts
Comparative Example 45 In Example 45, the intermediate layer made of zinc oxide was prepared using the following combination.
In place of the intermediate layer coating liquid, an intermediate layer with a thickness of 1.0 mm is provided.
Other than that, the photoreceptor of Comparative Example 45 was prepared in the same manner as in Example 45.
Created. ZnO powder 5 parts
Tanol 80 parts or more each
The characteristics of the photoreceptor were measured using an electrostatic copying paper tester (newly manufactured by Kawaguchi Electric).
5P-428 model) manufactured by Co., Ltd.), and was evaluated as follows. First, -5.2KV (or +5.6KV) discharge
Corona charging was carried out for 20 seconds at pressure, followed by IO seconds.
dark decay, then illuminated with 1(lQux tungsten light).
I shot it. Surface potential V2 (V) at 2 seconds and 20 seconds after the start of charging at this time
, V2o (V) and surface potential V3o after 10 seconds of dark decay
(V) and also optically attenuate V2O to half the potential.
Measure the exposure amount E□/2 (Qux-8ec) required to
Established. Note that the dark decay rate (D, D) is defined by the following formula:
Ru. D, D=v3. /■2゜Also, the surface potential after 20 seconds of the above exposure is taken as the residual potential vR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-6. 80 parts of water - 135 - 136 - Table 6 Example 48 Polyethylene terephthalate with aluminum vapor deposited.
BeO is used as the evaporation material on the film, and a resistance heating method is used.
Beryllium oxide with a thickness of 0.7 pm was made using the vacuum evaporation method.
A new middle layer was created. On top of this is a charge generation layer with the following composition.
Coating liquid and charge transport layer coating liquid are applied and dried one after another.
0.2〃thick charge generation layer and 22μm thick charge transport layer
was formed to produce an electrophotographic photoreceptor of the present invention. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 4 parts cyclohe
Xanone 2-butanone 300 parts 100 parts - 137 -- [Charge transport layer coating liquid] Charge transport material having the following structural formula: 25 parts Polyester 2 parts Tetrahydrofuran 270 parts
Example 49 Targera I ~ on an aluminum plate with a thickness of 0.2 mm
Using BeO, argon gas is introduced into the vacuum chamber, and a spa
Beryllium oxide with a thickness of 0.4 μm by the uttering method
An intermediate layer consisting of In this second, the charge of the following composition
Apply and dry the generation layer coating solution and charge transport layer coating solution in sequence.
After drying, a charge generating layer of 0,] μm and a charge generating layer of 17 μm were formed.
The electrophotographic photoreceptor of the present invention was created by shaping the cargo transport layer.
. [Charge generation layer coating liquid] 5 parts of a charge generation substance having the following structural formula [charge transport
IFl coating liquid] 25 parts of charge transport substance with the following structural formula 240 parts of methylene chloride
Example 50 Be on Targera 1 ~ on electroformed nickel with a thickness of 70 μm
An atmosphere where the partial pressure ratio of argon and oxygen gas is 1 using O.
An intermediate layer of beryllium oxide having a thickness of 0.339 to 140 μm was provided by sputtering under atmospheric pressure. this"
―, a charge generation layer coating liquid and a charge transport layer coating having the following compositions were applied.
A charge of 0.2 μm is generated by sequentially applying and drying the solution.
layer and a 20 μm charge transport layer to form an electron transport layer of the present invention.
A photographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 3 parts cyclohe
Xanone 2-butanone [Charge transport layer coating liquid] 200 parts of charge transport substance having the following structural formula 70 parts 25 parts Tetrahydrofuran 270 parts
Example 5] BeO is used as the evaporation material on a nichrome plate with a thickness of 0.2 mm.
A film thickness of 1.0 μm was obtained using the electron beam heating vacuum evaporation method.
An intermediate layer of beryllium oxide was formed. On top of this, a charge generation layer coating solution with the following composition and a charge transport layer are added.
The layer coating solution was applied and dried one after another to form a layer of 0 and 3 ftm each.
A charge generation layer and a charge transport layer of 18 μm were formed, and the present invention
A bright electrophotographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
Xanone Tetrahydrofuran [Charge Transport Layer Coating Solution] 200 parts of charge transport substance having the following structural formula 60 parts 30 parts 41 42 Tetrahydrofuran 250 parts
Example 52 Same as Example 50 on an aluminum plate with a thickness of 0.2 mm.
An intermediate layer made of beryllium oxide with a film thickness of 0.4 mm was prepared using the same method.
was formed. On top of this, a charge transport layer coating solution having the following composition,
Apply and dry the charge generation layer coating liquid and the protective layer coating liquid in sequence.
After drying, 19 charge transport layers each, 0, Ju+n charge generation
A green layer and a protective layer of 2 μm are formed, and the electrophotographic sensitivity of the present invention is
Created a light body. [Charge generation layer coating liquid] Charge generation substance having the following structural formula 25 parts tetra
Hydrofuran [Charge generating layer coating liquid] 270 parts of charge generating substance with the following structural formula 5 parts Cyclohexanone tetrahydrofuran [Protective layer coating liquid] 200 parts 100 parts Conductive titanium oxide Toluene n-butanol 90 parts 220 parts 60 parts -143- 44 Example 53 The same method as Example 48 was applied on a 0.2 m thick nickel plate.
to form an intermediate layer made of beryllium oxide with a film thickness of 1.2
did. On top of this, a charge transport layer coating solution with the following composition and a charge generating layer are added.
Apply the raw layer coating solution, intermediate layer coating solution, and protective layer coating solution in sequence.
Cloth/Dry charge transport layer of 20P each, charge of 0.2H
Forming a generation layer, a 0.2 μm intermediate layer and a 5 μm protective layer.
An electrophotographic photoreceptor of the present invention was prepared. [Charge transport layer coating solution] 30 parts of a charge transport substance having the following structural formula
Tyrene 1,2-dichloroethane [Charge generation layer coating solution] Trigonal selenium 150 parts 120 parts 10 parts Polyvinylcarbazole 2-butanone Toluene [Intermediate layer coating solution] 10 parts 60 parts 60 parts Methanol n-butanol [Protective layer coating Industrial solution] 70 parts 40 parts Tin oxide Toluene 2-butanone 80 parts 170 parts 100 parts Example 54 Same as Example 51 on a 0.3 mwn thick nickel plate.
An intermediate layer made of beryllium oxide with a thickness of 0.6 μm was formed using
Formed. On top of this, apply a charge transport layer coating solution with the following composition,
Apply and dry the protective layer coating solution and protective layer coating solution in sequence.
to form a charge transport layer of 22 μm, a charge generation layer of -145--146-0.3 μm, and a protective layer of 3 μm, respectively.
An electrophotographic photoreceptor of the present invention was prepared. [Charge transport layer coating liquid] 25 parts of a charge transport substance having the following structural formula
Tyrene [Charge generation layer coating solution] 260 parts 4 parts of the compound represented by the following structural formula [Protective layer coating solution] Titanium oxide 50 parts
Zu (H) 40 Part 1 ~ Rue
250 parts 2-butano
70 parts Example 55 Polyethylene terephthalate having Hastelloy as a conductive layer
Lay 1 - Thickness was applied to the film by the same method as in Example 49.
An intermediate layer made of beryllium oxide with a diameter of 0.6 μm was provided.
. On top of this, apply a two-part coating with the following composition and dry it.
A common photosensitive layer with a film thickness of 15 μm is provided, and the electrophotographic photosensitive layer of the present invention is
A euphotoreceptor was created. Toluylene-2,4-diisosiapho 1-cyclohexane
Non-2-butanone 0.2 parts 200 parts 80 parts Methylene chloride 650 parts The following composition
Compound represented by the formula 20 parts -147-H. Comparative Example 4-8.54 In Example 48.54, no intermediate layer was provided, respectively.
Other than that, Comparative Example 48,
54 photoreceptors were prepared. Comparative Examples 4.9, 50.53 In Examples 19 and 50.53, the intermediate layer had the following composition.
Instead of the intermediate layer coating liquid, an intermediate layer with a thickness of 0.3 μm was provided.
The rest was the same as in Examples 49, 50 and 53, and Comparative Example 49
. Photoreceptors Nos. 50 and 53 were prepared. Methanol 60 parts n-
Butanol 40 parts comparative example
51 In Example 51, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 0.5 μm was provided instead of
A photoreceptor of Comparative Example 51 was prepared in the same manner as Comparative Example 51. BeO powder 10 parts
1-Luylene-2,4-cyisocyane-1-0,1 sound [
S2-butanone 100 parts
Comparative Example 52 In Example 52, the intermediate layer made of beryllium oxide
Instead, use an intermediate layer coating liquid with the following composition and have a thickness of 1. Opm
A comparative example was prepared in the same manner as in Example 52 except that an intermediate layer was provided.
52 photoreceptors were prepared. BeO powder 5 parts
Tanol 60 parts n-buta
Nol 40 parts Comparative Example 55 In Example 55, the intermediate layer made of beryllium oxide
Instead, an intermediate layer coating liquid with the following composition was used, and the thickness was 2.07 mm.
A photoreceptor of Comparative Example 55 was prepared in the same manner as in Example 55, except that the intermediate layer in section m was provided. BeO powder 20 parts Toluene 20 parts or more
The characteristics of each photoreceptor were measured using an electrostatic copying paper tester (manufactured by Kawaguchi Electric).
The evaluation was made as follows using a newly manufactured model 5P-428). First, -5.2KV (or +5.6KV) 171 radiation
Electricity'/pressure b=-c, corona charging for 20 seconds, then
Dark decay for 10 seconds at
Irradiated with stainless steel light. Surface potential V2 (V) at 2 seconds and 15 seconds after the start of charging at this time
, V, 5 (V) and surface potential V2S after 10 seconds of dark decay
(V) and also optically attenuate Vzs to half the potential.
Measure the exposure amount E/2 (Qux-see) required to
Established. Note that the dark decay rate (D, D) is defined by the following formula:
Ru. D, D=V2. /V. In addition, the surface potential after 20 seconds of the above exposure is defined as the residual potential vR.
defined. Furthermore, charging and exposure under the conditions described in ``2'' were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were carried out again. Review
The evaluation results are shown in Table 7. Table 7 51-11521 Example 56 Polyethylene terephthalate with aluminum vapor deposited.
Using CaO as a target on the film, the target was placed in a vacuum chamber.
Introducing rugone gas and using sputtering method to obtain a thickness of 0.3
An intermediate layer of calcium oxide was provided. on this
Charge generation material with the following composition" two parts and charge transport layer coating solution in this order.
Next, apply and dry to form a 0.2-thick charge layer and 22
The electrophotographic photoreceptor of the present invention is formed by forming a charge transport layer with a thickness of μs.
It was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts cyclohe
Xanone 2-butanone [Charge transport layer coating liquid] 250 parts 100 parts Charge transport substance having the following structural formula 9 parts Tetrahydrofuran 81 parts Examples
57 Ca target on a 0.2 mm thick aluminum plate
An atmosphere where the partial pressure ratio of argon and oxygen gas is 1 using O.
Oxidation to a thickness of 0.4 μm by sputtering under atmospheric pressure
An intermediate layer of calcium was provided. On top of this, the following group
The charge generation layer coating liquid and the charge transport layer coating liquid were sequentially applied.
After coating and drying, a charge generation layer of 0.1 μm and 17
The electrophotographic photoreceptor of the present invention is formed by forming a charge transport layer of μm in thickness.
Created. [Charge generation layer coating liquid] Trigonal selenium 10 parts Polyvinyl
Nilcarbazole 10 parts. 2-butanone 60 parts-
153- 54- I.Luene [Charge generation layer coating liquid] 60 parts of charge generation substance having the following structural formula 10 parts Methylene chloride 80 parts Examples
58 Thickness: 70 mm on electroformed nickel.
O is used, and the partial pressure ratio of argon and oxygen is Ar10□=47
Thickness 0 by sputtering method in an atmosphere of 1
, :'l pm of calcium oxide was set up.
I got it. On top of this, a charge generation layer coating solution with the following composition and a charge transport layer are added.
The layer coating solution is applied and dried one after another, each with a charge of 0.2 μm.
A generation layer and a charge transport layer of 20 μm were formed, and the present invention
An electrophotographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 8 parts cyclo
Xanone 2-butanone [Charge transport layer coating liquid] 300 parts of charge transport substance with the following structural formula] 20 parts 10 parts Polycarbonate -10 parts (Teijin Kasei Kyu Panfy I-1-1300) Tetrahydride
LoFlan 75 parts Example 59 Shiko on a nichrome plate with a thickness of 0.2nrn, same as Example 56
rJ made of calcium oxide with a film thickness of 0.5 μm was prepared using the same method.
A y-interlayer was formed. On top of this, a charge generation layer of Sengonchi Kumiho
Apply and dry the coating solution and charge transport layer coating solution in 11 steps.
and a charge generation layer of 0 and 3 pm and a charge generation layer of 18 μm, respectively.
An electrophotographic photoreceptor of the present invention was prepared by forming a cargo transport layer. [Charge generation layer coating liquid] Charge generation substance cyclohexanone tetrahydrofuran having the following structural formula [Charge transport layer coating liquid] 5 parts of charge transporting substance having the following structural formula Example 58 and 5 parts were coated on a 0.5-thick aluminum plate. same
Intermediate film made of calcium oxide with a film thickness of 0.67+m
Created a layer. Second, apply a charge transport layer with the following composition.
Apply liquid, charge generation layer coating liquid, and protective layer coating liquid in sequence.
・Dry to form a charge transport layer of 19 μm and 0.3 μm respectively.
A charge generation layer and a protective layer of 2 μm are formed, and the charge generation layer of the present invention is
A child photographic photoreceptor was created. [Charge transport layer coating liquid] Charge transport material having the following structural formula 7 parts 200 parts 200 parts 25 parts Tetrahydrofuran [Charge generation layer coating liquid] Charge generating substance having the following structural formula 80 parts 3 parts Tetrahydrofuran Example 60 220 parts 1 157- Charge transport substance with the following structural formula 10 parts cyclohexanone tetrahydrofuran [protective layer coating liquid] 100 parts 40 parts Conductive titanium oxide 90 parts Toluene
220 parts n-pig
Knoll 60 parts Example 61 On a 0.2 mm thick nickel plate, the same one as Example 56
An intermediate layer made of calcium oxide with a thickness of 0.2 μm is formed using
Formed. On top of this, apply a charge transport layer coating solution with the following composition,
Apply the load-generating layer coating liquid, intermediate layer coating liquid, and protective layer coating liquid in this order.
Next, apply and dry a charge transport layer of 20 μm each, 0.2
- charge generation layer, 0.2 intermediate layer and 5H protective layer
was formed to produce an electrophotographic photoreceptor of the present invention. [Charge transport layer coating solution] Methylene chloride 1,2-dichloroethane [Charge generation layer coating solution] 50 parts of charge generation substance having the following structural formula 30 parts 7 parts 1 - Louisene-2,4-diisocyanate tetrahydro
Furan 4-methyl-2-pentanone [Intermediate layer coating liquid] 0.2 parts 400 parts 100 parts Alcohol-soluble polyamide (Amiran CM-8000 manufactured by Toshi ■) 2 parts 59 -160- Methanol n-butanol [Protective layer coating Industrial solution] 70 parts 40 parts Compound represented by the following structural formula 20 parts Tin oxide 80 parts Toluene
170 parts 2-pig
Non 100 parts Example 62 Polyethylene terephthalate having Hastelloy as a conductive layer
The same method as in Example 57 was applied to the rate film to a thickness of 0.
An intermediate layer of 6-calcium oxide was provided. above this
A coating liquid with the following composition was applied and dried to obtain a dry film thickness of 15 μm.
The electrophotographic photoreceptor of the present invention is prepared by providing a eutectic complex photosensitive layer of m.
Created. Comparative Example 56.60 In each of Examples 56 and 60, no intermediate layer was provided.
Comparative Example 56. was prepared in the same manner as Example 56.60 except for
Sixty photoreceptors were made. Comparative Example 59.62 In Example 59.62, the intermediate layer was an intermediate layer having the following composition.
In place of the coating liquid, an intermediate layer with a thickness of 0.3 mm was used.
Photoreceptor of Comparative Example 59.62 as in Example 59.62
It was created. Methanol 60 parts n-bu
Tanol 40 parts Comparative Example 5
7 In Example 57, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
-16 except that an intermediate layer with a thickness of 0.5 μm was provided instead of
1- -162- A photoreceptor of Comparative Example 57 was created in the same manner as Example 57.
. CaO powder] 0 parts A photoreceptor of Comparative Example 61 was prepared. CaO powder 20 parts toluylene-2,/I-diisocyanate-1-0, 1 part 2
-Butanone 1.00 parts ratio
Comparative Example 58 In Example 58, the intermediate layer made of calcium oxide
Instead, use an intermediate layer coating liquid with the following composition, and the thickness is 1.0 μm.
A comparative example was prepared in the same manner as in Example 58 except that an intermediate layer was provided.
Fifty-eight photoreceptors were prepared. CaO powder 5 parts
Tanol 60 parts n-buta
Nol 40 parts Comparative Example 61 In Example 61, the intermediate layer made of calcium oxide was
Instead of the intermediate layer coating liquid with the following composition, an intermediate layer with a thickness of 2.0 μm was used.
Toluene was prepared in the same manner as in Example 61 except that a layer was provided.
20 parts 0'' of each photoreceptor
The characteristics were measured using an electrostatic copying paper tester (Kawaguchi Electric Seisakusho theory 5P-
428 type) and was evaluated as follows. First, -5.2KV (or +5.6KV) discharge
Pressure discharge, coronamer; conduct pressure for 20 seconds, then 10
Dark and dark decay for seconds, then 10 Qux tungsten light
Irradiated. Surface potential V2 (V) at 2 seconds and 20 seconds after the start of charging at this time
, V2o (V) and surface potential v3o after 10 seconds of dark decay
(v) and also optically attenuate V2O to half the potential.
Exposure amount required to achieve
e) was measured. In addition, the dark decay rate (D, D) is expressed by the following formula:
defined. D, D''V30/V20 63- 164- Also, the surface potential after 20 seconds of the above exposure is taken as the residual potential VR.
defined. Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-8. Table 8 Example 63 Polyethylene terephthalate with aluminum vapor deposited
Using MgO as the evaporation material on the film, electron beam heating
magnesium oxide with a thickness of 1.1 μm using the vacuum evaporation method
An intermediate layer consisting of This second one generates a charge with the following composition.
Apply and dry the raw layer coating liquid and charge generation layer coating liquid in sequence.
Each 0.2 μm thick charge generation layer and 22 μm thick charge
A transport layer was formed to produce an electrophotographic photoreceptor of the present invention. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 4 parts cyclo
Xanone 2-butanone C charge transport layer coating liquid] 1.50 parts 110 parts -165- -166- 25 parts of charge transport substance having the following structural formula Tetrahydrofuran 280 parts
Example 64 0.2mm thick aluminum plate” Second, target
Using MgO in an atmosphere with a partial pressure ratio of argon and oxygen of 1
An oxide mask with a thickness of 0.3 μm was deposited using the sputtering method.
An intermediate layer made of gnesium was formed. On top of this, below
The charge generation layer coating solution and the charge transport layer coating solution of the composition were sequentially added.
After coating and drying, a charge generation layer of 0.1 pm and 1
Seven charge transport layers were formed to form an electrophotographic photoreceptor of the present invention.
Created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula 3 parts tetra
Hydrofuran [Charge Transport N Coating Solution] 250 parts of charge transport substance with the following structural formula 25 parts Methylene chloride 240 parts
Example 65 MgO is added as an evaporation material on electroformed nickel with a thickness of 70 μm.
Electron beam processing is performed while introducing oxygen gas into the vacuum chamber.
Magnesium oxide with a thickness of 0.7 μm is produced using a thermal vacuum evaporation method.
An intermediate layer consisting of the following layers was formed. On top of this, add an electric current of the following composition.
Apply the charge generation layer coating liquid and the charge transport layer coating liquid in sequence.
Dry to form a charge generating layer of 0.2 mm and 20/Im respectively.
A charge transport layer is formed to produce an electrophotographic photoreceptor of the present invention.
Ta. -1167-- [Charge generation layer coating liquid] Trigonal selenium polyvinylcarbazole 2-butanone toluene [Charge generation layer coating liquid] Charge generation substance of the following structural formula 10 parts 10 parts 60 parts 60 parts 25 parts Layer and 18 □ A charge transport layer of □□ is formed, and the charge transport layer of the present invention is
A child photographic photoreceptor was created. [Charge generation layer coating liquid] Charge generation substance with the following structural formula: 5 parts tetrahydrogen
Dorofuran 250 parts Example 66 On a nichrome plate with a thickness of OJnwn, Mg on Targera 1-
Sputtering is performed by introducing argon gas into the vacuum chamber using O.
Magnesium oxide with a film thickness of 0.2/111 by the ring method
We created a middle layer consisting of: Next, add the following composition on top of this.
Apply the charge generation layer coating solution and the charge transport layer coating solution in sequence.
Cloth/Dry, each generates a charge of 0.3/111 cyclohex
Sanon Tetrahydrofuran [Charge Transport Layer Coating Solution] 150 parts of charge transport material having the following structural formula 150 parts 30 parts -169- -170- Tetrahydrofuran 300 parts carried out
Example 67 Polyethylene terephthalate with Hastelloy as conductive layer
A second film was prepared in the same manner as in Example 64 to a thickness of 0.
An intermediate layer of 5 μm of magnesium oxide was provided. child
Apply a coating liquid with the following composition on top and dry it to determine the dry film thickness.
A eutectic complex photosensitive layer with a thickness of 15 μm is provided, and the electrophotographic sensitivity of the present invention is
Created a light body. An intermediate layer was formed. In this "-, charge transport with the following composition
Apply layer coating solution, charge generation layer coating solution, and protective layer coating solution in sequence.
, coated and dried, charge transport layer of 19 μm each, 0.3 μm
A charge generation layer of m and a protective layer of 2 μm were formed, and the present invention
An electrophotographic photoreceptor was prepared. [Charge transport layer coating solution] 30 parts of a charge transport substance having the following structural formula
Tyrene 650 parts Structural formula below
Compound represented by 20 parts tetrahydrofura
[Charge generation M coating liquid] 300 parts of charge generation substance having the following structural formula, 4 parts Example 68 Example 66 and
Using the same method, a film of magnesium oxide with a thickness of 0.4 μm was prepared.
171-172 Cyclohexanonetetrahydrofuran [Protective layer coating solution] 170 parts 1.00 parts Charge transport material with the following structural formula 28 parts Conductive titanium oxide 90 parts Toluene
220 parts n-pig
Knoll 60 parts Example 69 On a 0.2 mm thick nickel plate, in the same manner as Example 63.
Intermediate layer made of magnesium oxide with a film thickness of 0.8 μm
was formed. On top of this, a charge transport layer coating solution having the following composition,
charge generation layer coating liquid, intermediate layer coating liquid and protective layer coating liquid.
A charge transport layer of 20 pm and a charge transport layer of 0.0 pm were sequentially coated and dried.
2 charge generation layers, 0.2μm intermediate layer and 5 offshore protection layers.
A protective layer was formed to produce an electrophotographic photoreceptor of the present invention. [Charge transport layer coating solution] Methylene chloride 1,2-dichloroethane [Charge generation reverse layer coating solution] 200 parts of a charge generation substance having the following structural formula 60 parts 5 parts Toluylene-2,4-diisocyaphor 1-tetrahydro
Furan 4-methyl-2-pentanone [Intermediate M coating liquid] 0.3 parts 150 parts 100 parts 73 -174- Methanol n-butanol 70 parts 40 parts [Protective layer coating liquid] Tin oxide 80 parts Toluene
170 parts 2-pig
Non-100 copies Example 70 Example 65 and
From magnesium oxide with a film thickness of 0.9 parts m by the same method.
I created a middle layer. On top of this, charge transport with the following composition
Apply layer coating solution, charge generation layer coating solution, and protective layer coating solution in sequence.
, coated and dried to form a charge transport layer of 22n each, 0.3 parts m
The charge generation layer of the present invention and the protective layer of 3C are formed.
A child photographic photoreceptor was created. [Charge transport layer coating solution] 30 parts of a charge transport substance having the following structural formula
Tyrene [Charge generating layer coating liquid] 250 parts of charge generating substance with the following structural formula 4 parts Toluylene-2,4-diisocyapho-1-cyclohexane
Non-2-butanone [protective layer coating liquid] 0.1 part 100 parts 120 parts 175- 76- Titanium oxide 50 parts Oxidation
Tin(II) 40 parts torr
En 250 parts 2-Pig
Non 70 parts Comparative Example 63
．． 70 In Examples 63 and 70, no intermediate layer was provided, respectively.
Other than that, Comparative Example 63.
Seventy photoreceptors were made. Comparative Example 64, 66.69 In Example 64, 66.69, the intermediate layer had the following composition.
Instead of the intermediate layer coating liquid, an intermediate layer with a thickness of 0.5 μm was provided.
The rest was the same as in Examples 64, 66, and 69, and Comparative Example 64
A photoreceptor having a diameter of 66.69° was prepared. In Example 65, the intermediate layer was coated with an intermediate layer coating liquid having the following composition.
Example except that an intermediate layer with a thickness of 0.5 μm was provided instead of
A photoconductor of Comparative Example 65 was prepared in the same manner as Comparative Example 65. MgO powder 10 parts
Luylene-2,4-diisocyapho-1 to 0.1 part
2-butanone 100 parts
Comparative Example 67 In Example 67, the intermediate layer made of magnesium oxide
Instead, use an intermediate layer coating liquid with the following composition, and the thickness is 1.0-
A comparative example was prepared in the same manner as in Example 67 except that an intermediate layer was provided.
67 photoreceptors were prepared. MgO powder 5 parts Water Methanol 150 parts 200 parts Comparative Example 65 Methanol 60 parts N-butyl
Tanol 40 parts Comparative Example 6
8 In Example 68, medium-17 made of calcium oxide
7-7 Replace the interlayer with an interlayer coating liquid with the following composition, and make a layer with a thickness of 2.0 μm.
A comparative example was prepared in the same manner as in Example 68 except that an intermediate layer was provided.
Sixty-eight photoreceptors were prepared. CaO powder 20 parts
The dark decay rate (D, l)) is defined by the following equation. D, D=Vzs/L, s Also, the surface potential after 20 seconds of -1- placement light is the residual potential v11
It was defined as . Furthermore, charging and exposure under the above conditions were performed simultaneously for 30 minutes.
After fatigue, the same measurements as above were performed again. evaluation
The results are shown in Table-9. I-Luene 20 parts or more-
) The characteristics of each photoreceptor in 1 were measured using an electrostatic copying paper tester
The evaluation was made as follows using the newly manufactured Denki Seisaku 5P-7128 model).
I valued it. First, -5.2KV (or +5.6KV) (7)
Discharge/ Pressure discharge and corona charging for 20 seconds, then
dark decay for 10 seconds, then ]0Qux tungsten
irradiated with light. At this time, the surface potential V at 1 second and 15 seconds after the start of charging, (V)
, V, 5 (V) and the surface potential after 10 seconds of dark decay, V2.
．． (V) and v2. light attenuation to half potential
The exposure amount E1/□ ((lux-sec) required to
was measured. Note that 79 1.80 [Effects of the Invention] According to the present invention, after repeated use of the photoreceptor; lit:
It becomes possible to prevent deterioration of mold retention. In other words, image density decreases in copying machines, printers, etc.
Density unevenness, fog, or background during reverse development.
Good images without skin stains can be obtained.

[Brief explanation of the drawing]

1 to 6 are schematic cross-sectional views of an electrophotographic photoreceptor according to the present invention.

Claims (1)

[Claims] (1) In an electrophotographic photoreceptor comprising a photosensitive layer provided on a conductive substrate, tin oxide, titanium oxide, indium oxide, iron oxide, An electrophotographic photoreceptor comprising an intermediate layer made of at least one selected from lanthanum oxide, zinc oxide, beryllium oxide, calcium oxide, and magnesium oxide.