JPH07281462A - Electrophotographic photoreceptor and electrophotographic device with same - Google Patents

Abstract

PURPOSE:To ensure practical high sensitivity characteristics and stable potential characteristics in repetitive use by incorporating a specified styryl compd. and a specified triarylamine compd. into a photoreceptive layer. CONSTITUTION:In an electrophotographic photoreceptor with a photoreceptive layer on the electric conductive substrate, a styryl compd. represented by formula I and a triarylamine compd. represented by formula II are incorporated into the photoreceptive layer. In the formula I, X is -CH2-CH2- or -CH=CH-, each of R1 and R2 is alkyl which may have a substituent, aralkyl, an arom. cyclic group or a heterocyclic group, each of R3 and R4 is H, halogen, alkyl which may have a substituent or alkoxy and Ar1 is an arom. cyclic group which may have a substituent or a heterocyclic group. In the formula II, each of Ar2-Ar4 is phenyl and at least one of them has two 1-4C alkyl groups.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member and an electrophotographic apparatus equipped with the electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, inorganic photoconductive materials such as selenium, cadmium sulfide and zinc oxide have been widely used as electrophotographic photoreceptors. Although these have some basic characteristics, they have problems such as difficulty in film formation, poor plasticity, and high manufacturing cost. Further, the inorganic photoconductive substance is generally highly toxic, and there are great restrictions in production and handling.

On the other hand, the electrophotographic photosensitive member using the organic photoconductive material has many advantages such as supplementing the above-mentioned drawbacks of the inorganic photosensitive member and has attracted attention, and many proposals have been made so far.
Some have been put to practical use. As such an organic photoreceptor, a charge transfer complex formed of a photoconductive polymer represented by poly-N-vinylcarbazole and a Lewis acid such as 2,4,7-trinitro-9-fluorenone. An electrophotographic photosensitive member containing as a main component has been proposed. These organic photoconductive polymers are superior to the inorganic photoconductive polymers in terms of lightness, film-forming property, etc., but in terms of sensitivity, durability, stability due to environmental changes, etc., the inorganic photoconductive polymer is used. It is inferior to the elastic material and is not always satisfactory.

On the other hand, a function-separated type electrophotographic photosensitive member in which a charge generating function and a charge transporting function are shared by different substances, is remarkably improved in sensitivity and durability, which have been the drawbacks of conventional organic photosensitive members. Brought. Such a function-separated type electrophotographic photoconductor has the advantage that the material selection range of each of the charge generating substance and the charge transporting substance is wide, and that an electrophotographic photoconductor having arbitrary characteristics can be prepared relatively easily. There is.

As the charge generating material, various azo pigments, polycyclic quinone pigments, cyanine dyes, squaric acid dyes,
Pyrylium salt dyes and the like are known. Among them, azo pigments have been proposed as pigments having many structures from the viewpoints of strong light resistance, large charge generation ability, easy material synthesis, and the like.

As the charge transport material, a pyrazoline compound,
Hydrazone compounds, triphenylamine compounds, stilbene compounds and the like are known. These charge transport materials are required to be stable to light and heat, stable to ozone, NO _x , nitric acid, etc. generated by corona discharge, and have high charge transport ability. , High compatibility with organic solvents and binders, easy production, and the like. In addition, with the further increase in durability in recent years, a protective layer is provided on the photosensitive layer to improve durability,
When the photoconductor is stored for a medium period with a copying machine or a laser beam printer, cracks may occur in the charge transport layer, or the charge transport material may be crystallized or phase-separated. May be. Further, in a reversal development system corresponding to digitalization in recent years, since the primary charging and the transfer charging have opposite polarities, a so-called transfer memory having different charging properties depending on the presence or absence of transfer is generated, and density unevenness on an image is very likely to appear. Has become.

However, conventional electrophotographic photoreceptors using a charge transport material containing a low molecular weight organic compound satisfy some of the above problems and requirements, but none of them satisfy at a high level. Absent.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member having practically high sensitivity characteristics and stable potential characteristics in repeated use, cracks in the charge transport layer, charge Provided are an electrophotographic photosensitive member in which crystallization of a transport material does not occur, an electrophotographic photosensitive member in which a transfer memory is less likely to occur even in a reversal development system, and an electrophotographic apparatus provided with the electrophotographic photosensitive member are provided. It is to be.

[0009]

The present invention relates to an electrophotographic photoreceptor having a photosensitive layer on a conductive support, wherein the photosensitive layer is a styryl compound represented by the general formula (1) and a general formula (2).
The electrophotographic photosensitive member is characterized by containing a triarylamine compound represented by General formula (1)

[Chemical 15] In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2)

[Chemical 16] In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms.

Further, the present invention is an electrophotographic photoreceptor having a charge generating layer and a charge transporting layer on a conductive support, wherein the charge generating layer contains a phthalocyanine pigment represented by the general formula (3), and The transport layer comprises a styryl compound represented by the general formula (1) and a triaryl compound represented by the general formula (2).
The electrophotographic photosensitive member is characterized by containing a ruamine compound. General formula (3)

[Chemical 17] In the formula, R ₅ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an alkoxy group which may have a substituent, and n is an integer of 1 to 4. General formula (1)

[Chemical 18] In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2)

[Chemical 19] In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms.

Further, the present invention is an electrophotographic photoreceptor having a charge generating layer and a charge transporting layer on a conductive support, wherein the charge generating layer contains a trisazo pigment represented by the general formula (4), and The transport layer is composed of an electrophotographic photosensitive member characterized by containing a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (4)

[Chemical 20] In the formula, R ₆ represents an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group, and X ₁ represents a hydrogen atom, a halogen atom, an alkoxy group, a cyano group or a nitro group. General formula (1)

[Chemical 21] In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2)

[Chemical formula 22] In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms.

Further, the present invention is an electrophotographic photoreceptor having a charge generating layer and a charge transporting layer on a conductive support, wherein the charge generating layer contains a disazo pigment represented by the general formula (5), and The transport layer is composed of an electrophotographic photosensitive member characterized by containing a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (5)

[Chemical formula 23] In the formula, R ₇ represents a phenyl group which may have a substituent, and X ₂ represents a halogen atom. General formula (1)

[Chemical formula 24] In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2)

[Chemical 25] In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms.

The present invention further provides an electrophotographic photoreceptor having a charge generating layer and a charge transporting layer on a conductive support, wherein the charge generating layer contains a disazo pigment represented by the general formula (6), and The transport layer is composed of an electrophotographic photosensitive member characterized by containing a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (6)

[Chemical formula 26] In the formula, R ₈ represents a phenyl group which may have a substituent. General formula (1)

[Chemical 27] In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2)

[Chemical 28] In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms.

Specifically, in the general formula (1), the alkyl group is a group such as methyl, ethyl and propyl, the aralkyl group is a group such as benzyl, phenethyl and naphthylmethyl, the aromatic ring group is phenyl, Examples of groups such as naphthyl and heterocyclic groups include pyridyl, quinolyl, thienyl,
Examples of the substituent include a group such as furyl, and examples of the substituent include an alkyl group such as methyl, ethyl and propyl, an alkoxy group such as methoxy, ethoxy and propoxy, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom or a nitro group. Is mentioned.

In the general formula (2), examples of the alkyl group include groups such as methyl, ethyl, propyl and butyl.

In the general formula (3), the halogen atom is a group such as a fluorine atom, a chlorine atom and a bromine atom, the alkyl group is a group such as methyl, ethyl and propyl, and the alkoxy group is a group such as methoxy, ethoxy and propoxy. Groups.

In the general formula (4), the halogen atom is a group such as a fluorine atom, a chlorine atom and a bromine atom, the alkyl group is a group such as methyl and ethyl, the aralkyl group is a group such as benzyl and phenethyl, and an aromatic ring. Examples of the group include groups such as phenyl and naphthyl, examples of the heterocyclic group include groups such as pyridyl and quinolyl, and examples of the substituent include alkyl groups such as methyl and ethyl, alkoxy groups such as methoxy and ethoxy, and fluorine atoms. Examples thereof include a halogen atom such as a chlorine atom and a bromine atom, a cyano group or a nitro group.

In the general formula (5), the halogen atom is a group such as a fluorine atom, a chlorine atom and a bromine atom, and the substituent is, for example, an alkyl group such as methyl and ethyl, an alkoxy group such as methoxy and ethoxy, and a fluorine atom. , Halogen atoms such as chlorine atom and bromine atom, cyano group, nitro group and the like.

In the general formula (6), the substituent is
Examples thereof include alkyl groups such as methyl and ethyl, alkoxy groups such as methoxy and ethoxy, halogen atoms such as fluorine atom, chlorine atom and bromine atom, cyano group and nitro group.

Tables 1 to 9 show specific examples of the compounds represented by the general formulas (1) and (2) which are charge transport substances. However, it is not limited to these specific examples.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

Table 10 shows specific examples of the pigment as the charge generating substance represented by the general formula (3). However, it is not limited to these specific examples.

[Table 10]

Synthesis Example of Pigment Example P-1 In 100 g of α-chlornaphthalene, 5.0 g of o-phthalodinitrile and 2.0 g of titanium tetrachloride were heated and stirred at 190 ° C. for 3 hours and then cooled to 50 ° C. The precipitated crystals were separated by filtration to obtain a paste of dichlorotitanium phthalocyanine. Next, the paste was heated to 110 ° C. to produce N, N ′.
-Dimethylformamide 12. It was washed with 100 ml of methanol under stirring, then washed twice with 100 ml of methanol at 60 ° C., and separated by filtration. Further, the resulting paste was stirred in 100 ml of deionized water at 80 ° C. for 1 hour and filtered to obtain blue oxytitanium phthalocyanine crystals. Next, this crystal was dissolved in 35 ml of concentrated sulfuric acid, dropped into 1000 ml of deionized water at 20 ° C. under stirring, re-precipitated, filtered and thoroughly washed with water to obtain amorphous oxytitanium phthalocyanine. . Next, 2.0 g of this amorphous oxytitanium phthalocyanine was added to 20 ml of tetrahydrofuran,
After milling treatment with a sand mill for 20 hours together with 3.0 g of water, the crystals were separated by filtration to obtain blue oxytitanium phthalocyanine crystals.

Also in Pigment Examples P-2 to P-8, the compounds shown in Table 11 were used as raw materials, and in the other cases, Pigment Example P-1
It can be synthesized in the same manner as in.

[Table 11]

Tables 12 to 19 show specific examples of pigments which are the charge generating substances represented by the general formulas (4) to (6). However, it is not limited to these specific examples.

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

The photosensitive layer in the electrophotographic photoreceptor of the present invention comprises a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2).
It is composed of a combination of a seed charge transport material and an appropriate charge generation material. Examples of the structure of the photosensitive layer include the following forms. (1) Layer containing charge generating substance / layer containing charge transporting substance (2) Layer containing charge transporting substance / layer containing charge generating substance (3) Layer containing charge generating substance and charge transporting substance (4) Layer containing charge generating substance / layer containing charge generating substance and charge transporting substance

The charge generating layer contains as much charge generating substance as possible, and is a thin film layer, for example, a film of 5 μm or less, preferably 0.01 to 1 μm, in order to shorten the range of the generated charge carriers. A thick thin film layer is desirable.

The charge generating layer can be formed by dispersing the charge generating substance in a suitable binder resin and coating the same on a conductive support. The binder resin can be selected from a wide range of insulating resins.
It can be selected from organic photoconductive polymers such as N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. Preferably, polyvinyl butyral and polyallyl
(Condensation polymer of bisphenol A and phthalic acid), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, polyurethane, epoxy Resin, casein, polyvinyl alcohol
And polyvinylpyrrolidone. The resin contained in the charge generation layer is 80% by weight or less, preferably 40% by weight.
Weight% or less is suitable.

The solvent that dissolves these resins varies depending on the type of the resin, and is preferably selected from the type that does not dissolve the charge transport layer or the undercoat layer. Specifically, alcohols such as methanol, ethanol and isopropanol
, Acetone, methyl ethyl ketone, cyclohexane and other ketones, N, N-dimethylformamide, N, N
Amides such as dimethylacetamide, sulfoxides such as dimethyl sulfoxide, tetrahydrofuran, dioxane, ethers such as ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, chloroform, methylene chloride, dichloroethylene An aliphatic halogenated hydrocarbon such as carbon tetrachloride or trichloroethylene, or an aromatic compound such as benzene, toluene, xylene, ligroin, chlorobenzene or dichlorobenzene can be used.

As the coating method, a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a myver coating method, and a blade coating method. , Roller coating method, car
A method such as a tenting method can be adopted. Drying is preferably a method of drying by touching at room temperature and then drying by heating. The heat drying is carried out in a temperature range of 30 to 200 ° C. for 5 minutes to 2 hours with stopping or blowing.

The charge transport layer is electrically connected to the charge generation layer and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. have.

The charge transport layer can be formed by dissolving the styryl compound represented by the general formula (1) and the triarylamine compound represented by the general formula (2) together with a suitable binder resin and coating the solution. The binder resin is mixed with the styryl compound represented by the general formula (1) and the triarylamine compound represented by the general formula (2) in an amount of 10 to 10 parts by weight based on 100 parts by weight of the binder resin. It is preferably 500 parts by weight. Binder
Examples of the resin include acrylic resin, polyarylate,
Insulating resin such as polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber or poly Examples thereof include organic photoconductive polymers such as -N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. The thickness of the charge transport layer cannot be increased more than necessary because it has a limit to transport charge carriers, but it is 5 to 35 μm, preferably 8 to 30 μm. When the charge transport layer is formed by coating, the above-mentioned suitable coating method can be adopted.

As the conductive support, one having conductivity itself, for example, metal or alloy such as aluminum or aluminum alloy can be used. In addition, aluminum, aluminum alloy, indium oxide, tin oxide,
Indium oxide-tin oxide alloy or other plastic having a layer formed by a vacuum deposition method, conductive particles (for example, carbon black, silver particles, etc.) together with a suitable binder resin on the plastic or the metal support Examples thereof include a conductive support coated thereon, a conductive support obtained by impregnating plastic or paper with conductive particles, a plastic having a conductive polymer, and the like.

A barrier is provided between the conductive support and the photosensitive layer.
A function and an adhesive function can be provided. The undercoat layer is casein, polyvinyl alcohol, nitrocellulose
, Ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide and the like. The thickness of the undercoat layer is 0.1 to 5 μm, preferably 0.1.
It is 5 to 3 μm.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines, but also in laser beam printers and C
RT printer, LED printer, liquid crystal printer,
It can also be widely used in electrophotographic application fields such as laser plate making and facsimile.

The present invention also comprises an electrophotographic apparatus equipped with the electrophotographic photosensitive member of the present invention.

FIG. 1 shows a schematic structure of a general transfer type electrophotographic apparatus using the drum type photoreceptor of the present invention. In the figure, reference numeral 1 denotes a drum type photosensitive member as an image bearing member, and a shaft 1
It is rotationally driven around a at a predetermined peripheral speed in the arrow direction.
The photosensitive member 1 is uniformly charged at its peripheral surface by a charging unit 2 at a predetermined positive or negative potential in the course of its rotation, and then at an exposure unit 3 an optical image exposure L (slit exposure Laser beam scanning exposure). As a result, electrostatic latent images corresponding to the exposed image are sequentially formed on the peripheral surface of the photoconductor. The electrostatic latent image is then toner-developed by the developing means 4, and the toner-developed image is rotated by the transfer means 5 from a paper feeding portion (not shown) between the photosensitive body 1 and the transfer means 5. Then, the image is sequentially transferred onto the surface of the transfer material P that is fed in synchronization with the above. The transfer material P which has received the image transfer is separated from the surface of the photoconductor and is introduced into the image fixing means 8 where it is subjected to image fixing and printed out as a copy (copy). The surface of the photoconductor 1 after the image transfer is cleaned by the cleaning means 6 by removing the transfer residual toner, and is subjected to the charge removal processing by the pre-exposure means 7 to be repeatedly used for image formation. As a uniform charging means 2 for the photoconductor 1, a corona charging device is generally widely used. Also, as the transfer device 5, corona transfer means is generally widely used. As an electrophotographic apparatus, a plurality of constituent elements such as the above-mentioned photoconductor, developing means, and cleaning means are integrally combined and configured as an apparatus unit, and this unit is detachably attached to the apparatus main body. You may comprise. For example, the photosensitive member 1 and the cleaning means 6 may be integrated into one device unit, and the device body may be detachable by using a guide means such as a rail. At this time, the above-mentioned apparatus unit may be configured with a charging means and / or a developing means. When the electrophotographic apparatus is used as a copying machine or a printer, the light image exposure L uses reflected light or transmitted light from an original, or the original is read and converted into a signal by a laser. -Beam scanning,
This is performed by driving the light emitting diode array or the liquid crystal shutter array.

[0037]

【Example】

 Example 1 2.7 g of a disazo pigment represented by the following structural formula

[Chemical 29] Polyvinyl butyral (butyralization degree 65 mol%)
3.2 g of the solution was dissolved in 80 ml of cyclohexanone and dispersed in a sand mill for 30 hours to prepare a charge generation layer coating solution. This coating solution was applied on an aluminum sheet with a Mayer bar so that the film thickness after drying would be 0.22 μm to form a charge generation layer.

Next, as a charge transport material, Compound Example S-1 is used.
7 g of 3 and 3 g of T-11 and 9 g of polycarbonate (weight average molecular weight of 35,000) and 65 g of chlorobenzene.
g, and this solution was applied on the charge generation layer with a Mayer bar, and after drying, a charge transport layer having a film thickness of 20 μm was formed to prepare an electrophotographic photoreceptor.

The produced electrophotographic photosensitive member was manufactured by Kawaguchi Electric Co., Ltd.
Electrostatic copying paper tester Model-SP-428 was used to statically corona-charge at -5 KV, and then 1 in the dark.
After holding for 2 seconds, exposure was carried out with an illuminance of 20 lux, and charging characteristics were examined. As the charging characteristics, the surface potential (V ₀ ) and the exposure amount (E _1/5 ) required to attenuate the potential (V ₁ ) when dark-decayed for 1 second to 1/5 were measured.

Further, in order to measure the fluctuations of the light potential and the dark potential upon repeated use, the electrophotographic photosensitive member prepared was used as a cylinder for a photosensitive drum of a PPC copier NP-3825 manufactured by Canon Inc. , And 3,000 copies were made, and the bright part potential (V
_L ) fluctuation amount ΔV _L and dark part potential (V _D ) fluctuation amount ΔV
_D was measured. The initial V _D and V _L are -70, respectively.
It was set to be 0V and -200V.

As a test for promoting cracking of the photosensitive layer, finger oil was attached to the surface of the electrophotographic photosensitive member prepared,
It was allowed to stand at room temperature and normal pressure for 8 hours, and it was observed whether or not a crack was formed in the photosensitive layer.

Further, finger oil was adhered to the surface of the electrophotographic photosensitive member prepared as a test for promoting crystallization of the compound which is the charge transporting substance, and the compound was crystallized by leaving it at 75 ° C. for 1 week. It was observed whether or not.

Examples 2 to 8 Instead of the compound examples S-13 and T-3 used in Example 1, S-13 and T-19, S-39 and T-6, S-
39 and T-11, S-39 and T-15, S-52 and T-5, S-52 and T-14, S-52 and T-1.
Electrophotographic photosensitive members of Examples 2 to 8 were prepared in the same manner as in Example 1 except that No. 5 was used. With respect to each electrophotographic photosensitive member, the electrophotographic characteristics, cracks in the photosensitive layer, and crystallization of the compound as the charge transport material were evaluated by the same method as in Example 1.

Comparative Examples 1 to 3 Instead of the compound examples S-13 and T-3 used in Example 1, 10 g of the compound of Comparative Example 1 below, 10 g of the compound of Comparative Example 2 and the first of Comparative Example 3 were used. Comparative Examples 1 to 3 in the same manner as in Example 1 except that the compound 7g and the second compound 3g were used.
An electrophotographic photoconductor of was prepared. Compound used in Comparative Example 1

[Chemical 30] Compound used in Comparative Example 2

[Chemical 31] Compound used in Comparative Example 3

[Chemical 32]

[Chemical 33] With respect to each electrophotographic photosensitive member, the electrophotographic characteristics, cracks in the photosensitive layer, and crystallization of the compound as the charge transport material were evaluated by the same method as in Example 1.

[0045]

[Table 20]

As is clear from Table 20, the electrophotographic photosensitive member of the present invention is extremely superior to the electrophotographic photosensitive members of the comparative example in that cracks in the photosensitive layer and crystallization of the compound as the charge transporting substance do not occur. I understand that.

Example 9 4.5 g of N-methoxymethylated nylon (weight average molecular weight 30,000) and alcohol-soluble copolymerized nylon (weight average molecular weight 30,000910 g) were placed on an aluminum substrate.
Was dissolved in 90 g of methanol to apply it with a Mayer bar to form an undercoat layer having a thickness of 1 μm after drying.

Next, 3.9 g of the disazo pigment represented by the following structural formula was added.

[Chemical 34] A solution prepared by dissolving 4.2 g of phenoxy resin in 160 g of cyclohexanone was added and dispersed by a ball mill for 18 hours. This dispersion was applied on the undercoat layer by a blade coating method to form a charge generation layer having a thickness of 0.24 μm after drying.

Next, 5 g of Compound Example S-11 and 5 g of T-6 were added to a polycarbonate Z-type resin (weight average molecular weight 3
5,000) 10g dissolved in 75g chlorobenzene,
The prepared coating liquid was applied onto the charge generation layer by the blade coating method to form a charge transport layer having a film thickness of 20 μm after drying to prepare an electrophotographic photoreceptor.

The prepared electrophotographic photosensitive member was subjected to corona discharge of -5 KV. The surface potential (initial potential V ₀ ) at this time was measured. Further, the surface potential of this electrophotographic photosensitive member was measured after leaving it in the dark for 1 second. The sensitivity is the amount of exposure (E) necessary to attenuate the potential V ₁ after dark decay to 1/6.
It was evaluated by measuring _1/6 : μJ / cm ² . At this time, as a light source, a ternary semiconductor laser of gallium / aluminum / arsenic (output 5 mW, oscillation wavelength 780
nm) was used.

Next, a reversal development type laser beam printer (trade name: LBP-) equipped with the same semiconductor laser as above.
A so-called transfer memory is prepared by attaching an electrophotographic photosensitive member made to a remodeled machine of SX, manufactured by Canon Inc., with the primary charging voltage when the transfer current is off as V _d1 and the primary charging voltage when the transfer current is on as V _d2. − (V _d1 −V _d2 ) was measured, and then an image forming test was performed. The conditions are the surface potential after primary charging −
700 V, surface potential after image exposure -150 V (exposure amount 10
μJ / cm ² ), transfer potential +700 V, development polarity is negative, process speed is 47 mm / sec, development condition (development bias) is −450 V, scan mode after image exposure is image scan, exposure before primary charging 8. The entire surface exposure to red of 0 lux · sec and image formation were performed by line scanning the laser beam according to the character signal and the image signal, and good prints were obtained for both the character and the image.

Evaluation of cracks in the photosensitive layer of the electrophotographic photosensitive member thus prepared and crystallization of the compound of the charge transport material was carried out in the same manner as in Example 1.

Comparative Examples 4 to 6 Instead of the compound examples S-11 and T-6 used in Example 9, 0 g of the compound of the following Comparative Example 4 and compound 1 of the Comparative Example 5 were used.
0 g and the first compound 8 g of Comparative Example 6 and the second compound 2
Electrophotographic photoreceptors of Comparative Examples 4 to 6 were prepared in the same manner as in Example 9 except that g was used. Compound used in Comparative Example 4

[Chemical 35] Compound used in Comparative Example 5

[Chemical 36] Compound used in Comparative Example 6

[Chemical 37]

[Chemical 38] With respect to each electrophotographic photoreceptor, electrophotographic characteristics, transfer memory, cracks in the photosensitive layer and crystallization of the compound as the charge transport material were evaluated by the same methods as in Example 9.

Examples 10 to 14 Instead of the compound examples S-11 and T-6 used in Example 9, S-11 and T-10, S-25 and T-13, S.
-25 and T-17, S-50 and T-5, S-50 and T-14 were used, and electrophotographic photoreceptors of Examples 10 to 14 were prepared in the same manner as in Example 9. With respect to each electrophotographic photoreceptor, electrophotographic characteristics, transfer memory, cracks in the photosensitive layer and crystallization of the compound as the charge transport material were evaluated by the same methods as in Example 9.

[0055]

[Table 21]

Example 15 3.4 g of 4- (4-dimethylaminophenol) -2,6-diphenylthiapyrylium perchlorate, 5 g of compound example S-19 and 5 g of T-16 were used together. 100 g of a toluene (50 parts by weight) -dioxane (50 parts by weight) solution of the polymerized polyester (weight average molecular weight of 46,000) was mixed and dispersed with a ball mill for 24 hours. This dispersion was applied onto an aluminum sheet with a Mayer bar and dried at 120 ° C. for 1 hour to form a photosensitive layer having a thickness of 10 μm to prepare an electrophotographic photosensitive member.

The initial electrophotographic characteristics of the electrophotographic photosensitive member thus prepared were measured in the same manner as in Example 1. V ₀ : -700V, V ₁ : -692V, E _1/5 : 4.9
Lux · sec Further, a crack and crystallization acceleration test of the photosensitive layer was conducted in the same manner as in Example 1, and it was found that the crack was 8
It was not observed at all even after a lapse of time, and the crystallization was 1
It was not recognized even after a week.

Example 16 An alcohol-soluble nylon (6-66-
610-12 quaternary nylon copolymer) 30% methano-
Solution was applied and dried to form an undercoat layer having a film thickness of 1.6 μm.

Next, 7 g of Compound Example S-31, 3 g of T-9 and 12 g of bisphenol A type polycarbonate (weight average molecular weight 28,000) were added to chlorobenzene (60).
Part by weight) -dichloromethane (20 parts by weight) dissolved in 75 g of the solution, and this solution was applied on the undercoat layer with a Mayer bar to form a charge transport layer having a thickness of 22 μm after drying.

Further, a disazo pigment 4 represented by the following structural formula
g and

[Chemical Formula 39] Polyvinyl butyral (degree of butyralization 63 mol%)
2.0 g was dispersed by a sand mill in 65 ml of tetrahydrofuran. This dispersion was applied onto the charge transport layer with a Meyer bar so that the film thickness after drying was 1.2 μm, and dried to form a charge generating layer, thereby preparing an electrophotographic photoreceptor.

The electrophotographic characteristics of the electrophotographic photosensitive member are shown in Example 1.
The measurement was performed in the same manner as in (However, the charge was positively charged). V ₀ : +705 V, V ₁ : +700 V, E _1/5 : 2.2
Looks seconds

Example 17 On an aluminum substrate, 4 g of N-methoxymethylated 6 nylon (weight average molecular weight 28,000) and 10 g of alcohol-soluble copolymerized nylon (weight average molecular weight 28,000) were added to 35 g of methanol and butanol. The solution dissolved in 65 g of the mixed solution was applied by dip coating, and after drying, an undercoat layer having a film thickness of 1 μm was formed.

Next, 5 g of Compound Example S-28, 5 g of T-2 and 12 g of bisphenol A type polycarbonate (weight average molecular weight 27,000) were added to chlorobenzene (50).
100 parts by weight) -dichloromethane (50 parts by weight) solution
And the solution was coated on the undercoat layer with a Mayer bar to form a charge transport layer having a thickness of 27 μm after drying.

Next, 55 g of an acrylic monomer represented by the following structural formula,

[Chemical 40] 35 g of tin oxide ultrafine particles having an average particle size of 400 angstrom before dispersion, 3 g of 2-methylthioxanthone as a photoinitiator, and 280 g of methyl cellosolve were mixed with a sand mill.
Dispersion was performed for 2 hours. Using this dispersion, a film was formed on the charge transport layer by a beam coating method, dried and then photocured with a high pressure mercury lamp at a light intensity of 8 mw / cm ² for 30 seconds to obtain a film of 2.1 μm. A protective layer was formed to prepare an electrophotographic photoreceptor.

The produced electrophotographic photosensitive member was observed with a transmission microscope while shining light from the back surface at an angle of 15 degrees, but cracks and crystallization of the charge transport material compound did not occur.

Example 18 An undercoat layer of 0.2 μm of vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed on an aluminum plate.

Next, 5 g of Exemplified Pigment P-1 was added to a solution prepared by dissolving 2 g of polyvinyl butyral (butyralization degree 70 mol%, number average molecular weight 35,000) in 95 ml of cyclohexane, and the mixture was mixed with a sand mill at 22 Time dispersed. This dispersion was applied on the undercoat layer with a Mayer bar so that the film thickness after drying was 0.4 μm, and dried to form a charge generation layer.

Next, 2.5 g of Compound Example S-4 and T-3 were used.
And 2.5 g of bisphenol Z-type polycarbonate (viscosity average molecular weight 25,000) and 70 g of chlorobenzene.
The solution was dissolved in ml, and this solution was applied on the charge generation layer with a Mayer bar so that the film thickness after drying was 19 μm, and dried to form a charge transport layer, thereby preparing an electrophotographic photoreceptor.

The prepared electrophotographic photosensitive member was manufactured by Kawaguchi Electric Co., Ltd.
Electrostatic copying paper tester Model-SP-428 was used to statically corona-charge at -5 KV, and then 1 in the dark.
After holding for 2 seconds, exposure was carried out with an illuminance of 2 lux to examine charging characteristics. As the charging characteristics, the surface potential (V ₀ ) and the exposure amount (E _1/5 ) required to attenuate the potential (V ₁ ) when dark-decayed for 1 second to 1/5 were measured. V ₀ : -700V, V ₁ : -689V, E _1/5 : 0.6
0 looks seconds

Further, the electrophotographic photosensitive member is used as a cylinder of an electrophotographic copying machine equipped with a -5.6 KV corona charger, an exposure optical system, a developing device, a transfer charger, a static elimination exposure optical system and a cleaner. It was pasted and the image characteristics were examined. This copying machine is constructed so that an image can be obtained on a transfer sheet as the cylinder is driven. The image evaluation was performed in an environment where the humidity was 10%, the temperature was 5 ° C and the humidity was 50%, the temperature was 18 ° C and the humidity was 80%, and the temperature was 35 ° C. In all the environments, a good image faithful to the original was obtained. . This image showed good image characteristics without blurring or blurring of the image even on the 10,000th sheet.

Examples 19 to 33 Electrophotographic photoreceptors corresponding to Examples 19 to 33 were prepared in the same manner as in Example 18 except that the exemplified pigments and the compound examples which were charge transport materials were combined as shown in the table. Created.

E _1/5 of each electrophotographic photosensitive member was measured. Moreover, the cylinder of the same copier as in Example 18 - paste the electrophotographic photosensitive member, and set the initial light-area potential and the (V _L) dark portion potential (V _D) -200 V, the -700V respectively, 1 The amount of fluctuations ΔV _L and ΔV _D of the light potential (V _L 10000) and the dark region potential (V _D 10000) after 10,000 times of use were measured. However, ΔV _L and ΔV _D are defined as V _L O and V _D 0, respectively, where the initial bright portion potential and dark portion potential are
ΔV _L = [V _L 10000] − [V _L O], ΔV _D = [V _D 1
0000]-[V _D O].

[0073]

[Table 22]

Comparative Examples 7 to 10 Instead of the compound of the charge transport material used in Example 18, 5 g of the compound of Comparative Example 7 represented by the following structural formula, 5 g of the compound of Comparative Example 8 and the first of Comparative Example 9 were used. Corresponding to Comparative Examples 7 to 10 in the same manner as in Example 18, except that the compound 3g, the second compound 2g, and the first compound 2g and the second compound 3g of Comparative Example 10 were used as the charge transport material. An electrophotographic photoreceptor was prepared and the charging characteristics were measured. Further, the potential fluctuation amount was measured in the same manner as in Example 19. Compound (H-1) of Comparative Example 7

[Chemical 41] Compound (H-2) of Comparative Example 8

[Chemical 42] Compound of Comparative Example 9 (H-3)

[Chemical 43]

[Chemical 44] Compound of Comparative Example 10 (H-4)

[Chemical formula 45]

[Chemical formula 46]

[0075]

[Table 23]

Comparative Examples 11 to 16 Example 1 was repeated except that the compounds as the charge transporting substances of Comparative Examples 7 to 10 were combined with the pigment examples as shown in Table 22.
In the same manner as in Example 8, electrophotographic photosensitive members corresponding to Comparative Examples 11 to 16 were prepared, and the charging characteristics and the potential fluctuation amount were measured.

[Table 24]

Example 34 An undercoat layer of 0.4 μm of vinyl chloride-maleic anhydride-vinyl acetate copolymer was formed on an aluminum plate.

Next, 5 g of Exemplified Pigment G-6 was added to a solution prepared by dissolving 2 g of polyvinyl butyral (butyralization degree: 60 mol%, number average molecular weight 20,000) in 95 ml of cyclohexane, and added with a sand mill at 18 Time dispersed. This dispersion was applied on the undercoat layer with a Mayer bar so that the film thickness after drying was 0.4 μm, and dried to form a charge generation layer.

Next, 2.5 g of Compound Example S-2 and T-7 were used.
And 2.5 g of bisphenol Z-type polycarbonate (viscosity average molecular weight 25,000) and 70 g of chlorobenzene.
The solution was dissolved in ml, and this solution was applied on the charge generation layer with a Mayer bar so that the film thickness after drying was 19 μm, and dried to form a charge transport layer, thereby preparing an electrophotographic photoreceptor.

The charging characteristics were measured in the same manner as in Example 18. V ₀ : -700V, V ₁ : -695V, E _1/5 : 1.0
4 looks / second

Further, in the same manner as in Example 18, the humidity of 10
%, Temperature 5 ° C and humidity 50%, temperature 18 ° C and humidity 80%,
Image evaluation was performed in an environment of a temperature of 35 ° C., and good images faithful to the original were obtained in any environment. This image showed good image characteristics without blurring or blurring of the image even on the 10,000th sheet.

Examples 35 to 53 Electrophotographic photoreceptors corresponding to Examples 35 to 53 were prepared in the same manner as in Example 34 except that the exemplified pigments and the compound examples which were charge transporting substances were combined as shown in the table. Created.

For each electrophotographic photosensitive member, E _1/5 was measured in the same manner as in Example 19, and further the amount of potential fluctuation was measured.

[0084]

[Table 24]

Comparative Examples 17 to 20 Instead of the compound of the charge transporting material used in Example 34, 5 g of the compound of Comparative Example 17 represented by the following structural formula, Comparative Example 1
Example 34 except that 5 g of the compound of Example 8, 2 g of the first compound of Comparative Example 19, 3 g of the second compound and 1 g of the first compound of Comparative Example 20 and 4 g of the second compound were used as the charge transport material. Similarly, electrophotographic photoreceptors corresponding to Comparative Examples 17 to 20 were prepared and the charging characteristics were measured. Furthermore, the potential fluctuation amount was measured in the same manner as in Example 35. Compound of Comparative Example 17 (J-1)

[Chemical formula 45] Compound of Comparative Example 18 (J-2)

[Chemical formula 46] Comparative Example 19 Compound (J-3)

[Chemical 47]

[Chemical 48] Compound of Comparative Example 20 (J-4)

[Chemical 49]

[Chemical 50]

[0086]

[Table 26]

Comparative Examples 21 to 31 Example 3 was repeated except that the compounds as the charge transporting substances of Comparative Examples 17 to 20 were combined with the exemplified pigments as shown in the table.
Electrophotographic photoreceptors corresponding to Comparative Examples 21 to 31 were prepared in the same manner as in Example 4, and the charging characteristics and the amount of potential fluctuation were measured.

[Table 27]

From the above results, it can be seen that the electrophotographic photosensitive member of the present invention is excellent in sensitivity and repetitive potential characteristics.

[0089]

EFFECT OF THE INVENTION The electrophotographic photoreceptor of the present invention contains a specific charge-transporting substance so as to have high sensitivity, repetitive charging,
During continuous image formation by exposure, the fluctuations in the light potential and the dark potential are small, and the durability is excellent.Furthermore, the transfer memory is extremely small even in the reversal development system, and cracks and charge transport in the photosensitive layer that cause image defects are caused. It has a remarkable effect that crystallization of a compound of a substance is extremely unlikely to occur, and further has a remarkable effect that it is highly sensitive and has excellent repetitive potential characteristics when combined with a specific charge generating substance.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a general transfer type electrophotographic apparatus.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Drum type photoconductor as an image bearing member (electrophotographic photoconductor of the present invention) 1a axis 2 corona charging device 3 exposure section 4 developing means 5 transfer means 6 cleaning means 7 pre-exposure means 8 image fixing means L optical image Exposure P Transfer material that received image transfer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03G 5/06 C 371

Claims (10)

[Claims] 1. An electronic copy having a photosensitive layer on a conductive support.
In the true photoconductor, the photosensitive layer is a layer represented by the general formula (1).
Tyryl compound and triaryl represented by general formula (2)
Electrophotographic photosensitive material containing an amine compound
body. General formula (1)Where X Is -CH₂ -CH₂ -Or-CH = CH-
Show, R₁ And R₂ Is an alkyl which may have a substituent
Group, aralkyl group, aromatic ring group or heterocyclic group, R
₃ And R_Four Has a hydrogen atom, a halogen atom, and a substituent
Represents an alkyl group or an alkoxy group, Ar₁ Is
The aromatic ring group or heterocyclic group which may have a substituent is shown. General formula (2)In the formula, Ar₂ , Ar₃ And Ar_Four Represents a phenyl group,
At least one of them has two carbon numbers from 1 to carbon number
It has up to 4 alkyl groups. 2. A charge generation layer and a charge transport layer on a conductive support.
In the electrophotographic photosensitive member having a transfer layer, the charge generation layer is
Contains a phthalocyanine pigment represented by the general formula (3),
The charge transport layer is a styryl compound represented by the general formula (1).
And a triarylamine compound represented by the general formula (2)
An electrophotographic photosensitive member containing a substance. General formula (3)Where R_Five Is hydrogen atom, halogen atom, cyano group, nit
B group, an alkyl group which may have a substituent or an alkoxy group
Shows a Si group, and n is an integer of 1 to 4. General formula (1)Where X Is -CH₂ -CH₂ -Or-CH = CH-
Show, R₁ And R₂ Is an alkyl which may have a substituent
Group, aralkyl group, aromatic ring group or heterocyclic group, R
₃ And R_Four Has a hydrogen atom, a halogen atom, and a substituent
Represents an alkyl group or an alkoxy group, Ar₁ Is
The aromatic ring group or heterocyclic group which may have a substituent is shown. General formula (2)In the formula, Ar₂ , Ar₃ And Ar_Four Represents a phenyl group,
At least one of them has two carbon numbers from 1 to carbon number
It has up to 4 alkyl groups. 3. An electrophotographic photoreceptor having a charge generation layer and a charge transport layer on a conductive support, wherein the charge generation layer contains a trisazo pigment represented by the general formula (4), and
An electrophotographic photoreceptor, wherein the charge transport layer contains a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (4) In the formula, R ₆ represents an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group, and X ₁ represents a hydrogen atom, a halogen atom, an alkoxy group, a cyano group or a nitro group. General formula (1) In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2) In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms. 4. An electrophotographic photoreceptor having a charge generation layer and a charge transport layer on a conductive support, wherein the charge generation layer contains a disazo pigment represented by the general formula (5), and the charge transport layer is An electrophotographic photoreceptor comprising a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (5) In the formula, R ₇ represents a phenyl group which may have a substituent, and X ₂ represents a halogen atom. General formula (1) In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2) In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms. 5. An electrophotographic photoreceptor having a charge generation layer and a charge transport layer on a conductive support, wherein the charge generation layer contains a disazo pigment represented by the general formula (6), and the charge transport layer is An electrophotographic photoreceptor comprising a styryl compound represented by the general formula (1) and a triarylamine compound represented by the general formula (2). General formula (6) In the formula, R ₈ represents a phenyl group which may have a substituent. General formula (1) In the formula, X represents —CH ₂ —CH ₂ — or —CH═CH—, and R ₁ and R ₂ represent an optionally substituted alkyl group, aralkyl group, aromatic ring group or heterocyclic group. , R
₃ and R ₄ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group which may have a substituent, and Ar ₁ represents an aromatic ring group or a heterocyclic group which may have a substituent. General formula (2) In the formula, Ar ₂ , Ar ₃ and Ar ₄ represent a phenyl group,
At least one of them has two alkyl groups having 1 to 4 carbon atoms. 6. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1. 7. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 2. 8. An electrophotographic apparatus provided with the electrophotographic photosensitive member according to claim 3. 9. An electrophotographic apparatus provided with the electrophotographic photosensitive member according to claim 4. 10. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 5. [0001]