JPS62276562A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance electric chargeability, photodecay sensitivity, and resistance to residual potential by forming an interlayer made of a heat hardenable resin containing a specified disazo pigment. CONSTITUTION:The interlayer of an electrophotographic sensitive body obtained by successively laminating the interlayer, a charge generating layer, and a charge transfer layer on a conductive substrate is made of the heat hardenable resin containing either or both of disazo pigments represented by formulae I and II in which A is a group represented by formula III, IV, or V; X is an aromatic ring, such as a benzene or naphthalene ring, or an indole ring; Ar1 is an aromatic ring, such as a benzene or naphthalene ring, or a hetero ring, such as dibenzofuran, or the like; each of Ar2 and Ar3 is an optionally substituted aromatic ring, such as a benzene or naphthalene ring; each of R1 and R3 is H, lower alkyl, or the like; and R2 is lower alkyl, carboxyl, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an electrophotographic photoreceptor whose electric percentage varies little depending on the environment.

[Conventional technology]

Conventionally, many attempts have been made to impart high chargeability, high sensitivity, and low residual potential to an electrophotographic photoreceptor formed by stacking a charge generation layer and a charge transfer layer. As one of these, it has been proposed to provide an intermediate layer to prevent charges of opposite polarity from being injected from the conductive substrate side into the highly sensitive charge generation layer during charging. For example,
7-6341.48-3544 and 48-12034
The issue has a cellulose nitrate resin intermediate layer, published in Japanese Patent Application Laid-open No. 48-4
7344.52-25638.58-30757.5B
-65945, 58-95351, 58-98739 and 6O-6625B have a nylon resin intermediate layer,
JP-A-48-26141 has a vinyl acetate resin intermediate layer, % JP-A-49-69552 and 52-10138 have a maleic acid-based resin intermediate layer, and JP-A-53-10 has a maleic acid resin intermediate layer.
No. 0240 discloses a polyvinyl alcohol resin intermediate layer.

In addition, intermediate layers containing various X-conducting additives in resin have been proposed in order to control the electrical resistance of the intermediate layer. For example, JP-A-51-65942 discloses an intermediate layer in which carbon or a chalcogen-based substance is dispersed in a curable resin, and JP-A-52-82238 discloses an incyanate-based curing agent by adding a quaternary ammonium salt. JP-A No. 55-11130451 discloses a thermopolymer intermediate layer containing a resistance modifier, and JP-A No. 58-58556 discloses a resin intermediate layer containing aluminum or tin oxide dispersed therein. JP-A No. 58-93062 has a resin intermediate layer to which an organometallic compound is added! vj Kaisho 58-93063.60-9
Nos. 7363 and 60111255 have a resin intermediate layer in which conductive particles are dispersed, and JP-A-59-84257.
Nos. 59-93453 and 60-32054 include TlO
A resin intermediate layer in which powders of No. 2 and 5n02 are dispersed is disclosed.

Furthermore, based on the idea of controlling charge mobility instead of electrical resistance, a resin intermediate layer containing an electron-accepting organic compound as a negative charge mobility substance has been proposed. For example, JP-A No. 53-89433 discloses an organic polymer photoconductor intermediate layer containing a polycyclic aromatic nitro compound;
No. 7 and No. 59-170846 disclose a resin intermediate layer containing an electron-accepting organic substance.

In addition, for the purpose of improving spectral sensitivity,
No. 65852 discloses an invention in which a selenium-based charge generation layer having high photosensitivity to short wavelengths is laminated, and an organic charge transfer layer having high photosensitivity to long wavelengths is laminated thereon.

[Problems to be solved by the present invention]

However, the above-mentioned photoreceptor having an intermediate layer made only of resin was created in order to control high band characteristics and low residual potential by the electric resistance of the intermediate layer.
The ratio Ω of ~1014 is Ωα An insulating resin with relatively low electrical resistance is used as the intermediate layer, but in order to improve the charging property, it is necessary to increase the thickness of the intermediate layer, and the thickness of the intermediate layer must be increased after exposure. Conversely, in order to lower the residual potential, it is necessary to make the intermediate layer thinner, so it has been extremely difficult to satisfy both the conditions of high band strength and low residual potential. In addition, these resin intermediate layers are easily affected by moisture in the air, resulting in high charge and high residual potential at low temperatures and low humidity, and low charge and low residual potential at high temperatures and high humidity.)
However, there was a problem in that the characteristics varied significantly depending on the environment.

In addition, in a photoreceptor having a resin intermediate layer containing a four-electrode additive, the electrical resistance of the intermediate layer is controlled, but the electrical resistance of the intermediate layer is Since this affects the electrical characteristics of the photoreceptor, it has been difficult to satisfy both the conditions of high chargeability and low residual potential of the photoreceptor. In addition, in terms of environmental characteristics, conductive additives are easily affected by moisture in the air, so they cannot satisfy both the conditions of high chargeability and low residual potential, similar to the above-mentioned intermediate layer made of resin only. There wasn't.

Furthermore, although the electrical properties of photoreceptors containing electron-accepting organic compounds in the resin intermediate layer have small fluctuations due to environment, since the electron-accepting organic compounds are easily soluble in various organic solvents, it is difficult to coat the photosensitive layer. There is a problem that the electron-accepting material 5! mixes from the intermediate layer into the charge-generating layer and the charge-transfer layer during drying, resulting in a decrease in light attenuation sensitivity. Since L has high crystallinity and low compatibility with resins, there is also the problem that crystals tend to precipitate during the photoreceptor manufacturing process.

On the other hand, there is a method of satisfying the condition of high sensitivity of the photoreceptor without providing an intermediate layer, but without the intermediate layer, the problem arises that the repeated use characteristics deteriorate.

[Means for solving problems]

Therefore, the present invention provides an electrophotographic photoreceptor that has good chargeability, high sensitivity, and low residual potential even at low temperatures and low humidity as well as high temperatures and high humidity, and also has excellent film forming properties for the layers that constitute the photoreceptor. The aim is to provide the following.

Therefore, the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor in which an intermediate layer, a charge generation layer, and a charge transfer layer are sequentially laminated on a conductive substrate, and the intermediate layer has the following general formula (I) and ( I')○ (However, in formulas (I) and (■'), A is a group represented by the following formula (I), (I1) or (ilo ゛・X・′ (r+ o QiD), In this formula, in (I+> and QiD, or an aromatic ring such as a benzene ring or a naphthalene ring,
It is a hetero i-= such as an indole ring, a carbazole ring or a benzofuran ring, or a substituted product thereof, and Ar1 is an aromatic ring such as a benzene ring or a naphthalene ring, a hetero ring such as a dibenzofuran ring, or an f-substituted product thereof. ,
Ar2 and Ar5 are aromatic rings such as a benzene ring or a 7talene ring, or substituted substances thereof, and R1 and R
5 is hydrogen, a lower alkyl group, a phenyl group, or a substituent thereof, and R2 is a lower alkyl group, a carboxyl group, or an ester thereof. It is characterized by being made of a synthetic resin.

The electrophotographic photoreceptor according to the present invention is formed by sequentially laminating an intermediate layer, a charge generation layer, and a charge transfer layer on a conductive substrate.

A conductive substrate is one whose purpose is to supply a charge of opposite polarity to the band charge to the substrate side, and whose electrical resistance is 10
A material having a resistance of 8 Ωα or less and capable of withstanding the film forming conditions of the intermediate layer, charge generation layer, and charge transfer layer can be used. Examples of these include At5Ni, Or % Zn s
The surfaces of electrically conductive metals and alloys such as stainless steel, inorganic insulating materials such as glass and ceramics, and organic insulating materials such as polyester, polyimide, phenolic resin, nylon resin, and paper can be coated by vacuum deposition, sputtering, spray painting, etc. By the way, Aj! s Ni, Or ,
Examples include those coated with an electrically conductive material such as Zn, stainless steel, carbon, 5N02, or N205 and subjected to conductive treatment.

The intermediate layer is a layer that prevents charge injection from the conductive substrate to the charge generation layer when the photoconductor is charged, and maintains the chargeability, and when the photoconductor is exposed, serves as one of the pairs of charges generated in the charge generation layer, that is, conductive. A layer that is required to move charges of opposite polarity to the conductive substrate side to the conductive substrate side.

This is especially necessary when the charge generation layer has high sensitivity since the chargeability of the charge generation layer deteriorates. These characteristics can be evaluated by measuring the chargeability of the photoreceptor, the light attenuation sensitivity, and the residual potential remaining after light attenuation.

The functions and effects required of the above intermediate layer are expressed by the above general formula (
This effect can be achieved by containing the azo pigments represented by I) and (■') in a dispersed state in a thermosetting resin. In this case, high chargeability, high sensitivity, and low residual potential were obtained even under low temperature/low humidity and high temperature/high humidity conditions.

The content of the azo pigments represented by the general formulas (I) and (I') is 30% by weight to 80% by weight, and 4ON
% to 70]ii1% is preferred.

Table 1 shows examples of azo pigments represented by general formulas CI) and (■').

Table 1 Specific examples of general formulas (I) and (I') General formula (I1 General formula (I') Pigment AA Pigment A A Pigment 4 A Pigment A A Thermosetting resins that can be used include, for example, active hydrogen (- OH
There is a thermal polymer of a compound containing a plurality of hydrogen groups such as a hydrogen group, -NH2 group, -NH group, and a compound containing a plurality of isocyanate groups and/or a compound containing a plurality of epoxy groups. Examples of compounds containing multiple active hydrogens include polyvinyl butyral, phenoxy resins, phenol resins, polyamides, acrylic resins containing monooccupied hydrogen such as hydroxymethyl methacrylate groups, and compounds containing multiple isocyanate groups. Examples of compounds containing epoxy groups include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and their prepolymers, and compounds containing multiple epoxy groups include bisphenol A.
Examples include molded epoxy resin.

Conventional methods for dispersing the general formula (I) and the azo pigment represented by There is a method using a miller, stone mill, etc.

When dispersing, first the azo pigment is dispersed in an organic solvent solution of a compound containing active hydrogen, and then a compound containing a plurality of incyanate groups and/or a compound containing a plurality of epoxy resins is added. That's it. This is because the dispersion process involves heat generation, so thermal polymerization in the dispersion process should be avoided. The intermediate layer is formed on the conductive substrate by a conventionally known coating method such as roll coating, dip coating, spray coating, or blade coating, followed by heating at 50°C to 200°C. Polymerization is performed to form an intermediate layer having a thickness α of 1 μm to 10 μm, preferably 15 to 2 μm.

The charge generation layer is a layer whose purpose is to generate and separate charges by imagewise exposure.

In the present invention, the charge generation layer uses organic dyes and pigments, crystalline selenium, or arsenic selenide as a charge generation substance, and the organic dyes and pigments include 7/cyanine pigments, disazo pigments, and trisazo pigments. Examples include pigments, k-nylene pigments, squalic ring dyes, azulenium salt dyes, and quinone condensed polycyclic compounds. Examples of disazo pigments and trisazo pigments include compounds represented by general formulas I-1, II-It and -m. Examples of pigments represented by general formula 11-I are shown in Table 2, examples of nn are shown in Table 3, and examples of Tl-m are shown in Table 4.

Table 2 Specific examples of general formula (II-1) Pigment shop A Pigment A A Pigment shop A Pigment shop A Table 3 Specific examples of general formula (ff-II) N=N-A Pigment A A Pigment shop A Pigment & A Pigment A A Pigment Black Pigment & A Table 4 Specific examples of general formula (II-III) Pigment A A Pigment A A Pigment A A Ct Pigment iP5. A Pigment Haruka A General formula ([-1), (II-II), and (If-I[
The azo pigment represented by ) is used after being dispersed in a resin or without a resin by adding an organic solvent and using the same method as above, such as a ball mill method. Pigments for dispersing these azo pigments include, for example, polyamide, polyurethane, polyester,
Condensation resins such as epoxy resins, polycarbonates, and polyethers, and polymers and copolymers such as polystyrene, polyacrylates, polymethacrylates, polyN vinylcarbazole, polyvinyl butyral, styrene-butadiene copolymers, and styrene-acrylonitrile copolymers. However, absolute fineness and adhesion are required. It is dispersed using the same dispersion means as for the intermediate layer, and is formed into a film on the intermediate layer by the same method and dried to form a charge generation layer having a thickness Q of 05 μm to 0.5 μm. The content of the azo pigment is preferably 6-0% by weight to 100% by weight.

The crystalline selenium particles and the arsenic selenide alloy particles are used after being dispersed in the electron-donating binder by a method similar to that shown in the description of the intermediate layer above, such as by ball milling. The crystalline selenium particles used here can be obtained by a known method, such as heating and dissolving high-purity selenium in a highly concentrated aqueous alkaline solution, dropping this into pure water, or neutralizing it with an acid to obtain crystalline selenium (hexagonal It can be made by precipitating it as a crystalline form. On the other hand, particles of arsenic selenide have, for example, Q, 01 Torr to I Torr.
It can be obtained by evaporating arsenic selenide in nitrogen or an inert gas.

Examples of electron-donating organic compounds for dispersing the crystalline selenium particles and arsenic selenide particles used in the present invention as the charge generation layer include polyvinylcarbazole and its derivatives (
For example, halogens such as chlorine and bromine in the carbazole skeleton,
Nitrogen-containing compounds such as polyvinylpyrene, oxadiazole, pyrazoline, hydrazone, diarylmethane, α-phenylstilbene, triphenylamine compounds, and diarylmethane compounds, etc. However, polyvinylcarbazole and its derivatives are particularly preferred. Further, these compounds may be used in combination. Even when used in combination, it is preferable to add other electron-donating organic compounds to polyvinylcarbazole and its derivatives. The reasons why polyvinylcarbazole and its derivatives are preferable are that they have a larger ionization potential than other electron-donating organic compounds, and because they are polymers themselves, they can be easily applied to form a charge transfer layer. reactor.

The content of the charge generating substance 'Ik is from 30% by weight to 9% by weight of the entire layer.
0% by weight. A charge generation layer having a film thickness cL of 2 μm to 5 μm is formed by forming a film on the intermediate layer and drying it in the same manner as for the intermediate layer.

The charge transfer layer provided on the charge generation layer causes the band to hold charges on its surface, and also moves the charges generated and separated in the stain charge generation layer upon exposure to combine with the held charges. This is the layer whose purpose is to In order to achieve the purpose of retaining electrical charges, high electrical resistance is required.
In addition, in order to achieve the purpose of obtaining a high surface potential using the retained charges, it is required that the dielectric constant be small and the charge mobility be good. In order to satisfy these requirements, an organic charge transfer layer containing an organic charge transfer substance as an active ingredient is used. Examples of organic charge transfer substances include:
PolyN vinylcarbazole compounds, pyrazoline compounds, α-phenylstilbene compounds, hydrazone compounds, diarylmethane compounds, triphenylamine compounds, divinylbenzene compounds, fluorene compounds, anthracene compounds, oxadiazole compounds Conventionally known compounds such as compounds and diaminocarbazole compounds can be used. These organic charge transfer substances other than monomers such as polyvinylcarbazole may be used as a binder by blending them into resins similar to those shown for the charge generation layer, such as polycarbonate. However, the resin used in the charge generation layer and the resin used in the charge generation layer do not need to be the same. Furthermore, a plasticizer is added to these as necessary. Such plasticizers include, for example, halogenated paraffins, dimethylnaphthalene, dibutyl 7
Examples include copolymers of polymers such as talate, dioctyl phthalate, tricresyl phosphate, and polyester. The charge transfer substance, the binder resin, and silicone oil (as a leveling agent in Form 83) were dissolved in an organic solvent, and a film was formed and dried in the same manner as the intermediate layer and the charge generation layer to form a film with a thickness of 5 μm or less. A 30 μm charge transport layer is formed on the charge generation layer.

The charge transfer substance to resin binder ratio is 2/8 to V2 weight ratio, and the amount of silicone oil to the resin binder is 0.0.
01 weight t% to 1fji%.

(Example) Example 1 When the charge generation layer contains a compound represented by the general formula (It-I) A glass pot with a diameter of 12 cIn is charged with a pot capacity of y2f.
jk diameter 1α alumina sintered ball and 1202 following resin liquids 1 and 1 (I5F exemplified azo pigments A22 and 1002)
Methyl ethyl ketone was added to the mixture for 72 hours. Then, add 1202 more methyl ethyl ketone
After additional injection and milling for 24 hours, while stirring the N2809 dispersion solution, 24? (7) The following TD
Methyl ethyl ketone in bath solution 401 was added dropwise to prepare the intermediate layer coating solution as a bath solution.

Resin liquid-1 Polyvinyl butyral (trade name EL-18 parts by weight manufactured by Tsukiki Kagaku) Cyclohexane 92 parts by weight TD solution Tolylene diisocyanate (TD) 10 parts by weight Methyl ethyl ketone 90 parts by weight Diameter 15
．． In the glass pot of 2, the diameter of pot capacity A is 1 cI.
A 2.5 wt% cyclohexanone solution of polyvinyl butyral (BIJ-1) of 1.4 DOF and 25 f of exemplified pigment boiling 60 were added.
Time milled. Then add 4 more cyclohexanone
08? After additional mixing for 24 hours, the dispersion solution 8002 was mixed with Tetrahydro 7 Run 5 while stirring.
oaf was added dropwise to prepare a charge generation layer coating solution.

An aluminum plate with a thickness of 0.3 that has been cleaned with perchlorethylene vapor is immersed in the above-mentioned intermediate layer coating solution, pulled down and coated by dip coating, and then heated and cured at a temperature of 130°C for 1 hour to obtain a film thickness. A 1.5 μm intermediate layer was formed. Next, the aluminum plate on which this intermediate layer was formed was immersed in the above charge generation layer coating; 5.
After the coating was applied by dip coating at a speed of 100.degree. C./sec, the charge generation layer was formed on the intermediate layer by heating and drying at a temperature of 130.degree. C. for 10 minutes. Next, this aluminum plate was immersed in a charge transfer layer coating solution consisting of the following components, pulled out and coated by dip coating, and then heated and dried at a temperature of 130°C for 1 hour to completely float the film.
A 2 μm photoreceptor was obtained.

Charge transfer layer coating liquid α-phenylstilbene charge transfer substance 1 ON part Polycarbonate (trade name Panlite C! 1400)
10 parts by weight silicone oil (product name KF-50)
0.0002 parts by weight tetrahydrofuran
80% Comparative Example 1 A photoreceptor was prepared in the same manner as in Example 1.

However, no intermediate layer was provided.

Comparative example 2 A photoreceptor was produced in the same manner as in Example 1.

However, resin liquid 3 consisting of the following components was used as a coating solution for the intermediate layer, and was applied by dip coating, and was heated and cured at a temperature of 160° C. for 1 hour to obtain an intermediate/d of 1.2 μm.

Resin liquid-6 Polyvinyl butyral (BL-1m Suikagakusha□□□ 4
8 parts by weight Tolylene diisocyanate (TD engineering)
14.5ffii part cyclohexanone
552 parts by weight methyl ethyl ketone 1
6o31i [L section comparative example 3 A photoreceptor was produced in the same manner as in Example 1.

However, a resin liquid 4 consisting of the following components was used as a coating solution for the intermediate layer, and the coating was applied by dip coating, and the intermediate layer was dried by heating at a temperature of 130° C. for 10 minutes to obtain an intermediate layer having a thickness of 1.2 μm.

Resin liquid-4 Nylon resin (cM-8000 manufactured by Toshisha) 8
Parts by weight: methanol 60 parts by weight Butanol: 32 parts by weight or more
and high temperature and high humidity (30°C, 90%) measurement conditions using a commercially available electrostatic copying paper tester ((Kyuyokuchi Electric Seisakusho 98P4).
28 type) to measure the surface potential vm after being charged by -6KV corona discharge for 20 seconds.
The surface potential VpQ was measured after being left in a dark place for 0 seconds. Next, the tungsten lamp light was applied to the surface of the photoreceptor at a rate of 4.5
lux, and the exposure ftFM until the vpO power was reached and the residual surface potential Vr after irradiation for 50 seconds were measured.

In addition, in order to investigate the special order for use of <<
After fatigue after 0 minutes of repetition o V'm, V'po %
K'k and v'r were measured.

The above results are briefly shown in Table 5.

Table 5 Low temperature/low humidity Example 1 1190 0.71 0.77 8 11
70 G, 69 0.75 12 Comparative Example 1 78
00.69 0.53 0 540 α18 α3
001 21150 Q, 61 α59102 12
70 0.40 Q, 571921 312800.
76 α58 2 1310 0.70 0.601
63 High temperature/high humidity fatigue before fatigue after fatigue Example 1
1160 0.67 Q, 76 3 1130 0
．． 64 0.78 711'f'11750α66
0.5004800.140.12 CJl 2112
00.600.6010012400.460.151
421311800.740.58010900.48
0.500 Example 2 When the charge generation layer contains a compound represented by the general formula (I[-n) In a glass pot with a diameter of 15 ( Resin liquid-5, an exemplary azo pigment of 25F, and thread 144 were added and milled for 48 hours.
The dispersion solution taken out after adding 80 and mixing for 24 hours is 950? Methyl ethyl ketone 7 while stirring
1 o? A charge-generating top coating solution was prepared by dropping the solution.

Resin liquid-5 Cyclohexanone 970 parts by weight An aluminum plate with a thickness of 0.3 mm that had been cleaned with perchlorethylene vapor was immersed in the intermediate/fi coating liquid prepared in Example 1, and then pulled out and subjected to dip coating. After finishing, it was heated and cured at a temperature of 130C for 1 hour to form an intermediate layer with a thickness of 1.5 μm.

Next, the aluminum plate on which this intermediate layer was formed was dipped in the above charge generation layer coating, and pulled up at a speed of 6/sec to apply the dip coating, and then heated and dried at a temperature of 130°C for 10 minutes to form the charge generation layer. was formed on the intermediate layer. Next, this aluminum plate was immersed in a charge transfer layer coating solution consisting of the following components, pulled up, dip coated, and then heated and dried at a temperature of 130° C. for 1 hour to obtain a photoreceptor with a total film thickness of 22 μm. .

Charge transfer layer coating liquid silicone oil (product name KF-50) 0.00
02 parts by weight Tetrahydro 7 run 801℃
Amount Comparative Example 4 A photoreceptor was prepared in the same manner as in Example 2.

However, there was no middle class.

Comparative example 5 A photoreceptor was produced in the same manner as in Example 2.

However, dip coating was carried out using the &4 fat liquid-5 described above as a coating solution for the intermediate layer, and heat curing was performed at 130° C./MW for 1 hour to obtain a film #1.2 μm intermediate layer.

Comparative example 6 A photoreceptor was produced in the same manner as in Example 2.

However, dip coating was carried out using the above-mentioned resin liquid-4 as a coating solution for the intermediate layer, and the intermediate layer was dried by heating at a temperature of 130° C. for 10 minutes to obtain an intermediate layer having a film thickness of 1.2 μm.

In the same manner as in Example 1, Vm before and after fatigue,
Vpo, H1112, and vr were measured.

The results are briefly shown in Table 6.

Table 6 Low temperature/low humidity example 21300 0.72 0.64 5 127
0 G, 69 0.62 7 Saizai j49800.
620.50 0 8800.29 0.43 01
512000.60 α58 98 12600.43
0.61 1831 614100.770.60
6 1430 [1800,95237 High temperature/high humidity fatigue before fatigue after fatigue Example 2 1
280 0.69 0.59 2 1240 0.6
4 0.60 5 Comparative example 4 820 0.56 0
．． 40 0 510 0.24 0.28 01
511800.590.571 (I1113000,4
80,561441610400,620,56010
600, 500, 531 Example 6 When the charge generation layer contains a compound represented by the general formula (T1) In a glass pot with a diameter of 15 mm, the charge generation layer is
An alumina sintered ball having a diameter of 1 cIL, 4002 of the resin liquid 5, and 25f of the exemplary azo pigment A262 were charged and milled for 48 hours.

After that, add 5802 more resin liquid-5 and further 1C2
Dispersion solution 950 taken out after milling for 4 hours? Methyl ethyl ketone 7102 was added dropwise while stirring, and the resulting solution was used as a charge transfer layer coating solution.

An aluminum plate with a thickness of 0.3 mm that had been cleaned with perchlorethylene vapor was immersed in the intermediate layer coating solution prepared in Example 1, pulled out, applied by dip coating, and then heated at a temperature of 130°C for 1 hour. It was cured to form an intermediate layer with a thickness of 1.5 μm. Next, the aluminum plate on which this intermediate layer was formed was dipped in the above charge generation layer coating, and pulled up at a speed of 6 steps/second to apply the dip coating, and then heated and dried at a temperature of 130°C for 10 minutes to form the charge generation layer. was formed on the middle layer. Next, this aluminum plate was immersed in a charge transfer layer coating solution consisting of the following components, pulled out and coated by dip coating, and then heated and dried at a temperature of 130°C for 1 hour to obtain a photoreceptor with a total film thickness of 22 μm. .

Charge transfer layer coating liquid Hydrazone-based charge transfer substance 10 parts by weight 2H5 Polycarbonate (trade name Panrai) C! 1400)
10ffi parts silicone oil (product name KF-50
) 0.0002 parts by weight Tetrahydrofuran 80 holes [Comparative Example 7 A photoreceptor was prepared in the same manner as in Example 3.

Comparative example 8 A photoreceptor was produced in the same manner as in Example 5.

However, the above-mentioned resin solution-3 was used as the coating solution for the intermediate layer, and the coating was applied by dip coating, and then heated and cured at a temperature of 130°C for 1 hour.
．． The middle layer had a diameter of 2 μm.

Comparative example 9 A photoreceptor was produced in the same manner as in Example 3.

However, the above-mentioned resin liquid-4 was used as the coating solution for the intermediate layer, which was dip coated, and then heated and dried at a temperature of 130° C. for 10 minutes to obtain an intermediate layer having a thickness of 1.2 μm.

In a similar manner to Example 1.2, pre-fatigue vm 5
v1) O, "12", and Vr were measured.

The results are shown in Table 7.

Table 7 Low temperature/low humidity vs. acid 1314000.87 1.23 161420
G, 88 1.25 30 Tsutsumi miscellaneous 1j71120α74
1.02 0 930 0.24 0.68 21
814100.89 1.221061500 0.6
8 1.022021 914000.86 1.20
81360 0.62 0.90208 High temperature/high humidity example 31380 0.85 1.18 5 132
0 α79 115 10 Comparative example 71100 0.7
2 1.03 0 760 cL21 0.56
01 813800.82 1.241161480
0.42 0.781831 912800.85
1.22 01200 0.40 0.76 6 Example 4 When the charge generation layer contains crystalline selenium particles, hydroxide is placed in a 100 m hexagonal flask) A 50 wt% aqueous solution of IJium 401 and a purity of 99.99 wt% 4.74 f of amorphous selenium particles were added thereto, and the mixture was stirred and dissolved at 85° C. for 3 hours.

Add pure water to this solution and get 60? The mixture was left at room temperature for 18 hours. Next, put 740 ml of pure water in an Erlenmeyer flask with Vc1t, and dropwise add the selenium solution while stirring it.
Diluted. Next, while stirring this solution, 25 drops of a 60% aqueous hydrogen peroxide solution were added to precipitate crystalline selenium particles. The crystalline selenium particles were washed five times with about 700-degree pure water and dried under reduced pressure at 50°C to obtain about 62 pure crystalline selenium particles. This product was confirmed to be hexagonal by X-ray diffraction.

Next, in a 50cc glass sample bottle, 0.361
(Aki inches) Stainless steel pole 140? and the crystalline selenium particles obtained above 1. Or and Resin Liquid 6 below (122) were added and milled to obtain a charge generation layer coating liquid.

Resin liquid-6 Polyvinylcarbazole (trade name: Rubican) 5 parts by weight Tetrahydrofuran 45 parts by weight Toyaene 45 parts by weight In the intermediate layer coating liquid prepared in Example 1 on an A3-thick aluminum plate washed with perchlorethylene vapor. After dipping it in water, pulling it up and applying it by dip coating, it was cured by heating at a temperature of 130° C. for 1 hour to form an intermediate layer with a thickness of 1.5 μm. A charge generation layer coating solution is applied with a blade onto this intermediate 1, and 10
After drying at 0° C. for 60 minutes, a charge generation layer having a thickness of 2 μm was laminated. Next, a charge transfer 1 coating liquid consisting of the following components was applied onto this charge generation layer with a blade, and the coating solution was coated with a blade at a temperature of 100°C.
After drying by heating for 0 minutes, a charge transfer layer having a thickness of 20 μm was laminated to form a photoreceptor.

Charge transfer layer coating liquid diamine (as a charge transfer substance) Polycarbonate (trade name Panrai 01400)
9 parts by weight silicone oil (product name KF-so) 0
．． 00D 1 part by weight dichloromethane 1
02 parts by weight Example 4-2 A photoreceptor was prepared in the same manner as in Example 4.

However, the charge transfer substance in the charge transfer layer coating solution was used as a comparative example.
10 A photoreceptor was produced in the same manner as in Example 4.

However, no intermediate layer was provided.

Comparative example 11 A photoreceptor was produced in the same manner as in Example 4.

However, dip coating was carried out using the above-mentioned resin liquid 3 as a coating solution for the intermediate layer, and the intermediate layer was cured by heating at a temperature of 160° C. for 1 hour to obtain a 1.2 μm thick intermediate layer.

Comparative example 12 A photoreceptor was produced in the same manner as in Example 4.

However, dip coating was carried out using the above-mentioned resin liquid 4 as a coating solution for the intermediate layer, and the intermediate layer was dried by heating at a temperature of 130° C. for 10 minutes to form an intermediate layer of 1.2 μm.

Comparative Example 13 A photoreceptor was produced in the same manner as in Example 4-2. However, no intermediate layer was provided.

Comparative Example 14 A photoreceptor was produced in the same manner as in Example 4-2. However, the intermediate layer was created in the same manner as in Comparative Example 11.

Comparative Example 15 A photoreceptor was produced in the same manner as in Example 4-2. However, the intermediate layer was created in the same manner as in Comparative Example 12.

In the same manner as in Examples 1.2 and 3, Vm s Vpo, E XI2, and Vr were measured before and after fatigue.

The results are shown in Table 8.

Table 8 Low temperature/low humidity #4-21260 0.77 Q, 85 13127
0 Q, 77 0.86 21$110 960
G, 39 G, 48 2 860 0.30 0.35
3! ' 111300 0.790.8610314
00 0.75 G, 892041 121150
0.530.56 61140 0.41 0.491
61# 131060 0.59 CL56 197
0 0.37 0.42 21141330 o, a
i O,899914400,760,92208#
151180 0.620.63 31190 0.
64 0.72142 High temperature/high humidity 111 1220 0.770.871001350
0.75 0.87146z 1210100.42
(I,474980[1,32[1,27101131
0100,580,5609700,340,4211
1412700,800,8810313600,78
0,891511159100,620,591900
0,380,465 Example 5 When the charge generation layer contains arsenic selenide The inside of a vacuum tank equipped with a nitrogen gas (purity 99.999%) inlet was reduced to 1O-2 Torr using an exhaust pump, and then Introduce nitrogen gas into the vacuum tank to increase the pressure inside the tank to 0.2~a
Maintain at 4 Torr. As in advance to the energized heating port
2Se3 alloy 202 is added and the temperature of the boat is set to 4.
The 〇2Be3 alloy is evaporated while maintaining the temperature between 20 and 430°C. After the alloy had evaporated, fine arsenic selenide powder deposited on the inner wall of the tank was brushed off and collected. This fine powder was colored and had a particle size of 0.1 to 1 μm in diameter and a spherical shape.

Next, in a glass sample bottle of 3Qec, Q, 36I
1''1IL (A inch) stainless steel pole 70f and the fine arsenic powder Q obtained above, the resin liquid 6 of 52 and 951 were added and milled to obtain a charge generation layer coating liquid.

An aluminum plate with a thickness of 0.3 mm, which had been cleaned with chili-chlorethylene vapor, was immersed in the intermediate layer coating solution prepared in Example 1, pulled out, dip-coated, and then heated at a temperature of 130°C for 1 hour. It was cured to form an intermediate layer with a thickness of 1.5 μm. A charge generation fVI coating liquid was applied with a blade onto this intermediate layer, and dried at 100° C. for 30 minutes to form a charge generation layer having a thickness of 2 μm. Next, a charge transfer layer coating solution consisting of the following components was applied onto this charge generation layer using a blade, and the temperature was increased to 100°C.
The photoreceptor was dried by heating for 60 minutes at a temperature of 20 μm and a charge transfer layer having a thickness of 20 μm was laminated thereon.

Polycarbonate (product name Panlite 01400)
9 parts by weight silicone oil (product name KF-50)
Q, 000 '1 part by weight dichloromethane
102 parts by weight Example 5-2 A photoreceptor was prepared in the same manner as in Example 5.

However, the charge transfer '@ quality in the charge transfer layer coating solution is N, N
'-diphenyl-N,N'-bis(2-methylphenyl)-C1,1'-biphenyl,)-4,4'-diamine.

Comparative example 16 A photoreceptor was produced in the same manner as in Example 5.

However, no intermediate layer was provided.

Comparative example 17 A photoreceptor was produced in the same manner as in Example 5.

However, dip coating was carried out using the above-mentioned resin liquid 3 as a coating solution for the intermediate layer, and the intermediate layer 7r- was cured by heating at a temperature of 160° C. for 1 hour to obtain an intermediate layer 7r- of 1.2 μm.

Comparative example 18 A photoreceptor was produced in the same manner as in Example 5.

However, dip coating was carried out using the above-mentioned resin liquid-4 as a coating solution for the intermediate layer, and the intermediate layer was dried by heating at a temperature of 160° C. for 10 minutes to obtain a 1.2 μm thick intermediate layer.

Comparative Example 19 A photoreceptor was produced in the same manner as in Example 5-2. However, no intermediate layer was provided.

Vm, VpO1E difference, and Vr before and after fatigue were measured in the same manner as in Examples 1.2.3 and 4.

The results are shown in Table 9.

Table 9 Low temperature/low humidity 5 1260 0.680.81 151250
0.66 Q, 80 2515-21250 α6
4 α78121230 0.6I Q, 75 23
Saikyo 161060 0.400.58 61020
α29 α378# 171440 [176Q
,951011530 0.69 [1901981
1813600,470,701912900,38Q
, 57 180# 19 990 0.36 α52
10 980 Q, 28 Q, 30 12 High temperature/high humidity Example 5 1270 0.65 Q, 80 8 12
50 CJ, 62 0.78 1215-21240
[163cL76 91210 Q, 59 0.7
5 14μ night 16 j0900.36 Q, 54 8
940 0.30 α4541 171380 Q,
76 Q, 94981480 α69 Q, 861
501 181330 Q, 44 α69121290
a3I Q, 41 28# 199700.3
1 Q, 49 6 900 α25 0.2.0 3
(Effects of the Invention) As explained above, according to the present invention, the charging property is excellent even at low temperatures and low humidity, as well as high temperatures and high humidity at °C, and the light attenuation sensitivity is high.
Furthermore, an electrophotographic photoreceptor having a low residual potential is provided.

[Brief explanation of drawings]

The drawing is a diagram showing a cross section of an electrophotographic photoreceptor according to the present invention. DESCRIPTION OF SYMBOLS 1... Conductive substrate, 2... Intermediate layer, 3... Charge generation layer, 4... Charge transfer layer. Patent applicant Ricoh Co., Ltd. - 2 others Procedural amendments August 27, 1986

Claims (1)

[Claims] In an electrophotographic photoreceptor in which an intermediate layer, a charge generation layer, and a charge transfer layer are sequentially laminated on a conductive substrate, the intermediate layer has the following general formulas (I) and (I')▲mathematical formula , chemical formulas, tables, etc. ▼ ( I ) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ ( I ′) (However, in formulas ( I ) and ( I ′), A is the following formula (i), (ii ) or (iii) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(i)▲There are mathematical formulas, chemical formulas, tables, etc.▼(ii)▲There are mathematical formulas, chemical formulas, tables, etc.▼The group represented by (iii) In formulas (i), (ii) and (iii), is an aromatic ring such as a benzene ring or a naphthalene ring, a hetero ring such as a dibenzofuran ring, or a substituted product thereof, Ar_2 and Ar_3 are an aromatic ring such as a benzene ring or a naphthalene ring, or a substituted product thereof, and R_1 and R_3 are A thermosetting resin containing one or both of the disazo pigments represented by hydrogen, a lower alkyl group, a phenyl group, or a substituent thereof, and R_2 is a lower alkyl group, a carboxyl group, or an ester thereof. An electrophotographic photoreceptor comprising: