JPS61292149A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to extremely reduce residual potential even after durability test by incorporating a specified polycyclic quinone type pigment in an electrostatic charge generating layer, and a specified hydrazone derivative in a charge transfer layer. CONSTITUTION:A laminate type electrophotographic sensitive body is prepared by forming on a conductive substrate the charge generating layer containing the polycyclic quinone type pigment represented by structural formula (I), and the charge transfer layer containing the hydrazone derivative represented by general formula (II) in which R1, R2 are each H, halogen, alkoxy, aryloxy, or optionally substituted amino; R3, R4 are each alkyl or aryl; each of R5, R6, R7, R8 is H, halogen, alkyl, alkoxy, aryloxy, or optionally substituted amino; and n is 0 or 1. When the charge transfer material is added to the charge generating layer, it is suitable to add the hydrazone derivative in an amount of <=10 times, preferably, 0.01-1 time the weight of the charge generating material from the viewpoints of high sensitivity, low residual potential, and stability against repeated uses.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an organic photoconductor, and particularly to an electrophotographic photoreceptor having a charge generation layer and a charge transport layer.

[Prior Art 1] Electrophotographic photoreceptors using inorganic photoconductors such as selenium, cadmium sulfide, and zinc oxide as photosensitive components have been known. On the other hand, since the discovery that certain organic compounds exhibit photoconductivity, many organic photoconductors have been developed. For example, organic photoconductive polymers such as poly-N-vinylcarbazole and polyvinylanthracene, low-molecular organic photoconductors such as carbazole, anthracene, pyrazolines, oxadiazoles, hydrazones, and polyarylalkane, and phthalocyanine pigments. Organic pigments and dyes such as , azo pigments, cyanine pigments, polycyclic pigments, perylene pigments, indigo dyes, thioindigo dyes, and methine squaric acid dyes are known. especially,
Organic pigments and dyes with photoconductivity are easier to synthesize than inorganic materials, and the variety of compounds that exhibit photoconductivity in the appropriate wavelength range has been expanded, so there are many photoconductive materials. Organic pigments and dyes have been proposed.

For example, US Patent No. 4123270, US Patent No. 424761
No. 4, No. 4251613, No. 42516144,
Same No. 4256821, Same No. 4260672, Same No. 4
No. 268596, No. 4278747, No. 4293
As disclosed in No. 628, etc., electrophotographic photoreceptors are known that use a disazo pigment exhibiting photoconductivity as a charge generation substance in a photosensitive layer that is functionally separated into a charge generation layer and a charge transport layer.

An electrophotographic photoreceptor using such an organic photoconductor can be produced by coating by appropriately selecting a binder, so it is possible to provide an extremely highly productive and inexpensive photoreceptor.
Moreover, it has the advantage that the sensitive wavelength range can be freely controlled by selecting the organic pigment.

A multilayer photoconductor obtained by laminating a charge transport layer and a charge generation layer mainly composed of a charge generation material has advantages over other single-layer photoconductors in terms of sensitivity and increased residual potential after durability tests. However, it was still not at a sufficient level.

[Problems to be Solved by the Invention] An object of the present invention is to improve the above-mentioned drawbacks and to provide a laminated electrophotographic photoreceptor with high sensitivity and extremely low residual potential even after a durability test.

[Means and effects for solving the problems] The present invention achieves the above object by forming a charge generation layer containing a charge generation material as a main component and a charge transport layer containing a charge transport material as a main component on a conductive support-L. In a laminated electrophotographic photoreceptor having two layers, a specific polycyclic non-pigment is used in the charge generation layer, and a specific hydrazone compound is used in the charge transport layer.

The present invention provides a multilayer electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are provided on a conductive support, in which the charge generation layer is comprised of a layer containing a polycyclic iron pigment of structural formula (I). , a hydrazone compound whose charge transport layer is represented by the general formula (II) (wherein R1 and R2 are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted 7-aryloxy or a substituted amino group, provided that at least one of Ro and R2 is a substituted amine group or an alkoxy group, and R1 and R+ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, provided that At least one of R3 and R is a substituted or unsubstituted aryl group, and R3 and R4 may complete a nitrogen-containing heterocycle, and R4, R7
and R represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted amino group, and n represents 0 or l). It is composed of an electrophotographic photoreceptor characterized by the following.

The present invention will be explained in detail below.

In the layered electrophotographic photoreceptor of the present invention, the charge generation layer contains as much charge generation material as possible in order to obtain sufficient absorbance, and efficiently injects the generated charge carriers into the charge transport layer. To make a thin film layer, e.g. 10%
Hereinafter, it is desirable that the thin film layer preferably has a thickness of 0°0f-tJL.

This means that most of the incident light is absorbed by the charge generation layer, generating many charge carriers, and that the generated charge carriers are injected into the charge transport layer without being deactivated by recombination or trapping. This is due to the need to do so.

The charge generating material used in the present invention is a polycyclic ironone pigment represented by the structural formula.

The charge generation layer can be formed by coating the above-mentioned pigment and, if necessary, a charge transport material together with a suitable binder (or without a binder) on a substrate, or by forming a vapor deposited film using a vacuum vapor deposition apparatus. can be obtained by

The binder that can be used when forming the charge generating layer by coating can be selected from a wide variety of insulating resins, and can also be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene.

Preferably, polyvinyl butyral, polyarylate (
polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinylpyridine, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol,
Insulating resins such as polyvinylpyrrolidone can be mentioned.

The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less.

The solvent that dissolves these resins varies depending on the type of resin, and is preferably selected from those that do not dissolve the underlying charge transport layer or subbing layer.

Specific organic solvents include methanol, ethanol,
Alcohols such as isopropanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N, N
-dimethylformamide, N.

Amides such as N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate,
Aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, etc., or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. .

Coating methods include dip coating, spray coating, spinner coating, bead coating,
This can be carried out using a coating method such as a Mayer bar coating method, a blade coating method, a roller coating method, or a curtain coating method.

For drying, it is preferable to dry to the touch at room temperature and then heat dry.

Heat drying can be carried out at a temperature of 30 to 200° C. for a period of time ranging from 5 minutes to 2 hours under static IF or blowing air.

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

At this time, this charge transport layer may be laminated on or under the charge generation layer.

The substance that transports charge carriers in the charge transport layer (hereinafter simply referred to as charge transport substance) is preferably substantially insensitive to the wavelength range of electromagnetic waves to which the charge generation layer is sensitive.

The term "electromagnetic waves" as used herein includes the broad definition of "light rays" including γ-rays, X-rays, far-infrared rays, and the like.

When the photosensitive liquid wall of the charge transport layer coincides with or overlaps that of the charge generation layer, charge carriers generated in both trap each other, resulting in a decrease in sensitivity.

The charge transport substance used in the present invention has the general formula (II)
It is a hydrazone compound represented by

In the formula, R1 and R2 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted amine group, provided that at least one of R1 and R2 is A substituted amine group or an alkoxy group, R3 and R4 are substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl group, provided that at least one of R3 and R4 is a substituted or unsubstituted aryl group. group, and R and R4 may complete a nitrogen-containing heterocycle, and R1, R2
and RI? represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted 7-mino group, and n represents O or l.

This hydrazone compound is a charge transporting substance that satisfies the conditions listed in L, and has particularly excellent properties in terms of sensitivity and durability.

Typical hydrazone compounds used in the present invention are illustrated below.

Further, in the present invention, the above-mentioned hydrazone compound used in the charge transport layer can be added to the charge generation layer.
The sensitizing effect becomes even more remarkable.

When a charge transport material is added to the charge generation layer, the hydrazone compound should be used in an amount of 10 times or less (weight ratio), preferably 0.01-1 times (weight ratio), of the charge generation material to provide high sensitivity, low residual potential, and repeatability. This is appropriate from the standpoint of stability.

To form a charge transport layer containing a hydrazone compound,
Film formation can be achieved by selecting an appropriate binder.

Resins that can be used as binders include, for example, acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, etc. Insulating resin or poly-N-vinylcarbazole,
Organic photoconductive polymers such as polyvinylanthracene and polyvinylpyrene may be mentioned.

Since the charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary.

Generally it is 5 to 30, but the preferred range is 8 to 2.
It is 0IL.

When forming the charge transport layer by coating, an appropriate coating method as described above can be used.

A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a substrate having a conductive layer.

As the substrate having the conductive layer, materials that are conductive themselves such as aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, platinum, etc. can be used. In addition, plastics (e.g., polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, Polyfluorinated ethylene, etc.), conductive particles (e.g. carbon black, silver particles, etc.) with a suitable binder and a base made of a plastic coated with a base, a base made of a plastic or paper impregnated with conductive particles, or a conductive polymer. Plastin resin or the like can be used.

A subbing layer having barrier and adhesive functions can also be provided between the conductive layer and the photosensitive layer.

The subbing layer consists of casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenolic resin, polyamide (nylon 6).
, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc.

The thickness of the undercoat layer is 0.1 to 40 #L, preferably 0.1
~3 wells is appropriate.

When using a photoreceptor in which a conductive layer, a charge generation layer, and a charge transport layer are laminated in this order, and the charge transport material in the charge transport layer is composed of an electron transport material, the surface of the charge transport layer must be positively charged; When exposed to light after being charged, electrons generated in the charge generation layer are injected into the charge transport layer in the exposed area, and then reach the surface and neutralize the positive charge, resulting in attenuation of the surface potential and an electrostatic contrast between it and the unexposed area. occurs.

A visible image can be obtained by developing the electrostatic latent image formed as in step 1 with a negatively charged toner.

This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc. and then developed and fixed.

Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor-1 is transferred onto an insulating layer of a transfer paper, and then visually imaged and fixed.

The type of developer, the developing method, and the fixing method may be any known ones or methods, and are not limited to specific ones or methods.

On the other hand, when the charge transport material is a hole transport material, it is necessary to charge the surface of the charge transport layer negatively, and when exposed to light after charging, holes generated in the charge generation layer are injected into the charge transport layer in the exposed area. , which then reaches the surface and neutralizes the negative charge, resulting in an attenuation of the surface potential and an electrostatic contrast with the unexposed area. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transport material is used.

The electrophotographic photoreceptor according to the present invention suffers from deterioration due to ultraviolet rays, ozone, etc., dirt from oil, etc., scratches from metal chips, etc., and damage to the photoreceptor from photoreceptor contact members such as developing members, transfer members, and cleaning members. A protective layer may be further provided on the charge generation layer for the purpose of preventing scratching.

In order to form an electrostatic latent image on this protective layer.

It is desirable that the surface resistivity is 10 11 Ω or more -L.

The protective layer used in the present invention is made of polyvinyl butyral, polyester, polycarbonate, acrylic resin, methacrylic resin, nylon, polyimide, polyarylate, polyurethane, styrene-butadiene copolymer, styrene-
It can be formed by dissolving a resin such as acrylic acid copolymer or styrene-7crylonitrile copolymer in a suitable organic solvent and coating the photosensitive layer and drying it. Moreover, additives such as ultraviolet absorbers can be added to the resin liquid. At this time, the film thickness of the protective layer is generally 0.05 to 20 IL,
Preferably it is in the range of 0.2 to 5 IL.

Hereinafter, the present invention will be explained according to examples.

Example 1 An ammonia aqueous solution of casein (casein 11, 2 g, 28% ammonia Ig, water 222 ml) was coated on an aluminum cylinder by dip coating, and dried to give a coated amount of 1.0 g/base undercoat layer. was formed. Next, 1 part by weight of the charge generating material of structural formula (I), 1 part by weight of butyral resin (Eslec BM-2, manufactured by Sekisui Chemical Co., Ltd.) and 30 parts by weight of isopropyl alcohol were dispersed for 4 hours using a ball mill disperser.

This dispersion was applied onto the previously formed subbing layer by a dip coating method and dried to form a charge generating layer. The film thickness was 0.31L.

Next, 1 part by weight of the above-mentioned hydrazone compound example (1), 1 part by weight of polysulfone (P1700, Union Carbide Attire), and 6 parts by weight of monochlorobenzene were mixed,
The mixture was stirred and dissolved using a stirrer.

This liquid was applied onto the charge generation layer by dip coating and dried to form a charge transport layer.

This film thickness was 1271 mm.

A corona discharge of 15 KV was applied to the photoreceptor thus prepared.

The surface potential (initial potential V) at this time was measured.

Furthermore, the surface potential of this photoreceptor was measured after it was left in a dark place for 5 seconds (dark decay Vj-).

Sensitivity was evaluated by measuring the exposure amount (E 1/21ux, 5ec) required to attenuate the potential Vt after dark decay to 1/2.

These results were as follows.

V6: -585V, V5: -575V, E 1/2:
6, 6 lux, sec Examples 2 to 5 Completely the same as Example 1 except that hydrazone compound examples (2) to (5) were used in place of hydrazone compound example (1) used in Example 1. A photoreceptor was prepared in a similar manner, and the characteristics of this photoreceptor were measured.

These results are shown below.

1 cliff 1 portrait 1 ruin Vo -V V -V E 1/2 l
ux 5ea2 (2) 580 570
8.53(a) 595 585 B.
s4 (4) 590 580 8.7
5 (5) [05907,4 Comparative Example 1~
6 The photoreceptors of Comparative Examples 1 to 6 were prepared in exactly the same manner except that the following comparative charge transport substances (1) to (6) were used in place of the hydrazone compound used in Example 1, and the charged Characteristics were measured.

C,H.

Charging characteristics 1 (1) 805 580 11
．． 22 (2) 590 570
8.83 (3) 585 5E15
9.04 (4) 1315 5
85 111.7.

5 (5) eoo
575 9. IB (8)
595 585 9.3 As is clear from the results of Examples and Comparative Examples, the laminated photoreceptor of the present invention has extremely high sensitivity compared to the photoreceptors of Comparative Examples 1 to 6. I understand.

Furthermore, the photoreceptors of Examples 1 to 5 were used in a copying machine (NP-150).
2. Image output using Canon (manufactured by Co., Ltd.)
Repeated 00 times.

As a result, good quality images were obtained even after repeating the test 20,000 times with each photoreceptor, indicating that the photoreceptor of the present invention has extremely excellent durability.

[Effect of the invention]

Claims (2)

[Claims] (1) In a laminated electrophotographic photoreceptor in which a charge generation layer and a charge transport layer are provided on a conductive support, the charge generation layer consists of a layer containing a polycyclic quinone pigment of structural formula (I), and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) Hydrazone compounds whose charge transport layer is represented by the general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 and R_2 are hydrogen atoms , halogen atom,
Represents a substituted or unsubstituted alkyl group, alkoxy group, substituted or unsubstituted aryloxy group, or substituted amino group, provided that at least one of R_1 and R_2 is a substituted amino group or alkoxy group, and R_3 and R_
4 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, provided that at least one of R_3 and R_4 is a substituted or unsubstituted aryl group, and R_3 and R_4 complete the nitrogen heterocycle. R_5, R_6, R_7 and R_8 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a substituted or unsubstituted aryloxy group or a substituted amino group, and n is 0 or 1. An electrophotographic photoreceptor comprising a layer containing: (2) The electrophotographic photoreceptor according to claim 1, wherein the charge generation layer contains a hydrazone compound represented by formula (II).