JPS6137620B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a layer containing a novel charge-transporting substance made of an oxime compound. The photoconductive process of an electrophotographic photoreceptor consists of (1) the process of generating electric charge by exposure to light, and (2) the process of transporting the electric charge. A selenium photosensitive plate is an example of performing (1) and (2) using the same material. On the other hand, a combination of amorphous selenium and poly-N-vinylcarbazole is well known as an example of performing (1) and (2) using separate substances. The method of performing (1) and (2) using separate substances expands the selection range of materials used for the photoreceptor, thereby improving the electrophotographic properties such as sensitivity and acceptance potential of the photoreceptor, and also improving the photoreceptor coating film production. It has the advantage that convenient substances can be selected from a wide range. Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as photoconductive substrates for photoreceptors used in electrophotography. Electrophotography has already been covered by Carlson's U.S. Patent No.
2297691, its electrical resistance changes depending on the amount of radiation received during image exposure.
A photoconductive material consisting of a support coated with an insulating substance is used in the dark. The photoconductive material is generally first given a uniform surface charge in the dark after dark adaptation for a suitable period of time. The material is then imagewise exposed to a pattern of radiation that has the effect of reducing the surface charge depending on the relative energy contained in different parts of the radiation pattern. The surface charge or electrostatic latent image thus left on the surface of the photoconductive material layer (photosensitive layer) then becomes a visible image when that surface is contacted with a suitable electrometric indicator, ie, toner.
Toner, whether contained in an insulating liquid or in a dry carrier, can be deposited on the surface of the photosensitive layer depending on the charge pattern. The deposited display material can be fixed by known means such as heat, pressure, and solvent vapor. The electrostatic latent image can also be transferred to a second support (eg, paper, film, etc.). It is likewise possible to transfer the electrostatic latent image to a second support and develop it there. Electrophotography is one of the image forming methods in which images are formed in this manner. The basic characteristics required of the photoreceptor in such electrophotography are (1) ability to be charged to an appropriate potential in the dark, (2) low charge dissipation in the dark, and (3) For example, the charge can be quickly dissipated by light irradiation. It is true that the conventionally used inorganic materials have many advantages, but also have various disadvantages. For example, selenium, which is currently widely used, fully satisfies the conditions (1) to (3) above, but the manufacturing conditions are difficult, the manufacturing cost is high, it is not flexible, and it cannot be processed into a belt shape. It also has disadvantages, such as being difficult to handle and being sensitive to heat and mechanical shock, requiring careful handling. Cadmium sulfide and zinc oxide are used as photoreceptors by dispersing them in a resin as a binder, but the smoothness and
Due to mechanical defects such as hardness, tensile strength, and abrasion resistance, it cannot be used repeatedly as it is. In recent years, electrophotographic photoreceptors using various organic materials have been proposed in order to eliminate the drawbacks of these inorganic materials, and some of them have been put into practical use. For example, poly-N-vinylcarbazole and 2.4.7
- A photoreceptor made of trinitrofluoren-9-one (US Pat. No. 3,484,237), a photoreceptor made of poly-N-vinylcarbazole sensitized with a pyrylium salt dye (Japanese Patent Publication No. 48-25658), a photoreceptor made of a dye and a resin. A photoreceptor whose main component is a eutectic complex
Publication No. 10735). In addition, a highly sensitive electrophotographic photoreceptor is a combination of a substance that generates electric charge when exposed to light (called a charge-generating substance) and a substance that can transport the generated electric charge (called a charge transporting substance). Proposed. For example, US Pat. No. 3,791,826 discloses a photoreceptor in which a charge transport layer is provided on a charge generating layer, and US Pat. No. 3,573,906 discloses a photoreceptor in which a charge transport layer is provided on a charge transport layer. Further, U.S. Pat. No. 3,764,315 describes a photoreceptor having a photosensitive layer having a charge generating material dispersed in a charge transporting material. Although many useful charge-generating substances have been proposed for this type of photoreceptor, the current situation is that very few truly useful charge-transporting substances have been proposed. A good charge-transporting material is one that sufficiently transmits light of a wavelength that causes charge generation from the charge-generating material, and that when it is charged, it can maintain a sufficient potential. It has the ability to quickly transport the charges generated by the process. As a result of extensive research, the present inventors discovered that compounds represented by the general formula (), (), or () described later are truly useful charge transport materials for electrophotographic photoreceptors. As a result, we have arrived at the present invention. An object of the present invention is to provide an electrophotographic photoreceptor having an electrophotographic photosensitive layer containing a novel charge transporting substance. Another object of the present invention is to provide an electrophotographic photoreceptor having an electrophotographic photosensitive layer with high sensitivity and low residual potential. Still other objects of the present invention are that it is stable against oxidation caused by ozone generated by corona charging, light, and heat, has little dark decay of potential, has little increase or fluctuation in residual potential due to repeated use, and has low sensitivity fluctuations. An object of the present invention is to provide an electrophotographic photoreceptor having a stable electrophotographic photosensitive layer. Still another object of the present invention is to provide an electrophotographic photosensitive layer which can be synthesized using non-toxic or less toxic raw material compounds and which contains a non-toxic or less toxic charge transport material. The object of the present invention is to provide an electrophotographic photoreceptor that has safe handling and disposal. Still another object of the present invention is to provide a stable charge transport layer that has high film strength, excellent uniformity, and less fatigue deterioration. The present invention provides an electrophotographic photoreceptor characterized by having a photoconductive composition containing an oxime compound represented by the following general formula (), (), or () and a photosensitive layer made of this photoconductive composition. It is related to. R ¹ is an alkoxy group, an aralkyloxy group, or

[Formula] represents a substituted amino group; R ¹⁰ and R ¹¹ are an alkyl group with or without a substituent, a phenyl group with or without a substituent, or R ¹⁰ and R ¹¹ are connected Represents a group capable of forming a heterocycle containing a nitrogen atom; R ¹⁰ and R ¹¹ may be the same or different; R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group, or a lower alkoxy group; R ⁴ represents a hydrogen atom, an alkyl group, a phenyl group with or without a substituent; R ⁵ represents a hydrogen atom, an alkyl group, an aralkyl group, Represents a phenyl group with or without substituents. A has 10 or more carbon atoms, with or without substituents such as halogen, alkyl group, lower alkoxy group, etc.
Represents 20 fused carbocycles or a monocyclic or fused 5-membered heterocyclic ring or fused 6-membered heterocyclic ring represented by the following structural formula;

【formula】 【formula】

Y and Z are S・O・N−R ⁹ (R ⁹ is 1 carbon number
to 4 alkyl groups) and may be the same or different atoms; R ⁶ and R ⁷ are the same or different groups and represent a hydrogen atom, an alkyl group, or an alkoxy group, or R ⁶ and Represents a group that can be linked with R ⁷ to form a benzene ring or a naphthalene ring; R ⁸ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a monoalkylamino group, a dialkylamino group, an amide group, or a nitro group, which may or may not have a substituent. may be; B represents an arylene group with or without a substituent. As the alkoxy group or aralkyloxy group of R ¹ , an alkoxy group having 1 to 12 carbon atoms, a carbon number 1
There are ~12 aralkyloxy groups, specific examples of which are methoxy, ethoxy, propoxy,
There are butoxy, octyloxy, and benzyloxy groups. R ¹ is

In the case of a substituted amino group represented by [Formula], R ¹⁰ and R ¹¹ may be an alkyl group having 1 to 12 carbon atoms without a substituent such as a methyl group, ethyl group, propyl group, or butyl group, or the following: There are alkyl groups having 1 to 12 carbon atoms having substituents such as: Substituents for the alkyl group having a substituent represented by R ¹⁰ and R ¹¹ include an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a hydroxy group, an aryl group having 6 to 12 carbon atoms, These include cyano groups and halogen atoms. Specific examples of alkyl groups having substituents represented by R ¹⁰ and R ¹¹ include (a) alkoxyalkyl such as methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methoxybutyl, propoxymethyl; b) aryloxyalkyl such as phenoxymethyl, phenoxyethyl, naphthoxymethyl, phenoxypentyl;
(c) Hydroxyalkyl such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyoctyl, hydroxymethyl, (d) Aralkyl such as benzyl, phenethyl, ω・ω-diphenylalkyl, (e) Cyanomethyl, cyanoethyl, cyanopropyl, Preferred are cyanoalkyls such as cyanobutyl and cyanoethyl, and (f) haloalkyls such as chloromethyl, bromomethyl, chloroethyl, promopentyl, and chlorooctyl. The phenyl group represented by R ¹⁰ and R ¹¹ may have a substituent, and specific examples of the substituent in the case of a phenyl group having a substituent include (a) carbon number 1;
~12 alkyl group, (b) alkoxy group having 1 to 4 carbon atoms, (c) aryloxy group having 6 to 7 carbon atoms, (d)
Acyl group having 2 to 8 carbon atoms, (e) alkoxycarbonyl group having 2 to 5 carbon atoms, (f) halogen atom, (g)
Monoalkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, (h) dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, (i) 2 carbon atoms
-4 amide groups, and (j) nitro groups. (a) As an alkyl group having 1 to 12 carbon atoms, methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, hexyl group, (b) Alkoxy group having 1 to 4 carbon atoms as methoxy group, ethoxy group, propoxy group, butoxy group, (c) as aryloxy group phenoxy group, o-, m- or p-tolyloxy group, (d) as acyl group,
Acetyl group, propionyl group, benzoyl group, o
-, m- or p-toluoyl group, (e) carbon number 2
to 5 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, (f)
Halogen atoms include chlorine, bromine, and fluorine atoms; (g) monoalkylamino groups substituted with alkyl groups having 1 to 4 carbon atoms include methylamino, ethylamino, and butylamino groups; (h) carbon atoms; Dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, N-methyl-N-ethylamino group as dialkylamino group substituted with 1 to 4 alkyl groups; (i) acetamido group, propion as amide group; Amide group, (j) Other substituents include nitro group. The heterocycle formed by connecting R ¹⁰ and R ¹¹ is preferably a heterocycle represented by the following structural formula.

【formula】 【formula】

【formula】

【formula】

[Formula] (This group is included in the general formula () group

Corresponds to [formula]. ) R ¹ is preferably a substituted amino group, and R ¹⁰ and
A substituted amino group in which R ¹¹ is a methyl group, ethyl group, benzyl group, phenyl group, or tolyl group is preferred. Particularly preferred are dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, N-ethyl-N-phenylamino group, and the like. As R ² and R ³ , hydrogen atom; chlorine atom,
Halogen atoms such as bromine and fluorine; alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl; 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy groups;
4 alkoxy groups, etc. Among them, hydrogen atoms, methyl groups, methoxy groups, etc. are preferred. Specific examples of R ⁴ include a hydrogen atom; methyl group, ethyl group, propyl group, butyl group, etc. having 1 to 1 carbon atoms;
4 alkyl groups and phenyl groups with or without substituents. The phenyl group having a substituent is the same as the phenyl group having a substituent represented by R ¹⁰ or R ¹¹ described above.
Preferred among R ⁴ are a hydrogen atom, a methyl group, an ethyl group, a phenyl group, and a p-(dimethylamino)phenyl group. R ⁵ is a hydrogen atom; carbon number 1 to 12, such as a methyl group, ethyl group, propyl group, octyl group, etc.
Alkyl group; benzyl group, phenethyl group, ω・
Examples include aralkyl groups having 7 to 24 carbon atoms such as ω-diphenylprokyl groups; and phenyl groups with or without substituents. The phenyl group having a substituent is the same as the phenyl group having a substituent represented by R ¹⁰ or R ¹¹ described above.
Particularly preferred among R ⁵ is benzyl group. The fused carbocyclic group represented by A includes fused carbocyclic groups having 10 to 20 carbon atoms such as 1-naphthyl group, 2-naphthyl group, 9-anthracenyl group, and 1-pyrenyl group. 5-membered complex ring represented by A

R ⁶ and R ⁷ in [Formula] are hydrogen atoms; alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl; carbon atoms such as methoxy, ethoxy, propoxy, and butoxy groups; Included are alkoxy groups of numbers 1 to 4 and groups capable of forming a benzene ring or a naphthalene ring by connecting R ⁶ and R ⁷ . fused heterocycle

[expression] or

R ⁸ in [Formula] is a hydrogen atom, an alkyl group with or without a substituent similar to the alkyl group with or without a substituent represented by R ¹⁰ or R ¹¹ above, and a carbon number of 1
-4 alkoxy group, C6-10 aryloxy group, C2-11 acyl group, C2-5
an alkoxycarbonyl group, an aryloxycarbonyl group having 7 to 11 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, and an amide group having 2 to 9 carbon atoms, or There are nitro groups, etc. These may or may not have a substituent. Methoxy, ethoxy, propoxy, butoxy groups as alkoxy groups having 1 to 4 carbon atoms; phenoxy, o-, m- or p-tolyloxy groups as aryloxy groups having 6 to 10 carbon atoms; 2 to 4 carbon atoms; As the acyl group of 11, acetyl group, propionyl group, benzoyl group, o-,
m- or p-toluoyl group; carbon number 2 to 5
As the alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group; carbon number 7 to 11
phenoxycarbonyl group, o-, m- or p-tolyloxycarbonyl group as aryloxycarbonyl group; chlorine atom as halogen atom,
As a monoalkylamino group substituted with a bromine atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms,
Methylamino group, ethylamino group, butylamino group, dialkylamino group substituted with an alkyl group having 1 to 4 carbon atoms, such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, N-methyl-N- An ethylamino group, an amide group such as an acetamide group or a propionamide group, and other substituents include a nitro group. Y and Z represent S, O or N- ^R9 .
R ⁹ is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. 2-furyl group, 2-thienyl group, 1-methyl-2-pyrrolyl group, 5-methyl-2-thienyl group as the 5-membered hetero ring represented by A; 2-benzo[b] as the fused 5-membered hetero ring thienyl group, 2-naphtho[2,3-b]thienyl group, 9-ethylcarbazol-2-yl group, dibenzothiophene-2
-yl group, fused 6-membered hetero ring, 2-phenoxathiinyl group, 10-ethylphenoxazine-3-
yl group and 10-ethylphenothiazin-3-yl group are preferred. More preferred among these are 5-methyl-2-thienyl group, 2-benzo[b]thienyl group, 9-ethylcarbazol-2-yl group, dibenzothiophen-2-yl group, and 10-ethylphenylene group. It is a notiazin-2-yl group. Specific examples of B include a phenylene group and a naphthylene group. When having a substituent, the substituent is
It is a group similar to R ² or R ³ . Specific examples of the oxime compound represented by the general formula (), () or () are shown below. A compound represented by the general formula (), () or () can be easily produced by a known method. That is, if necessary, a small amount of acid (acetic acid or inorganic acid) is added as a condensing agent, and hydroxylamines and the corresponding aldehyde or
Obtained by dehydration condensation with a ketone. However, the compound represented by the general formula () can be obtained by dehydration condensation of hydroxylamines and the corresponding dialdehyde or diketone. When using hydrochloride of hydroxylamines, it is preferable to use a mixed solvent with pyridine. Solvents include alcohols such as methanol and ethanol, aromatics such as benzene and xylene, hydrocarbons, dioxane, tetrahydrofuran,
N.N-dimethylformamide and the like can be used alone or in combination. By using a compound represented by the general formula (), () or () as a charge transport substance,
The film properties, durability, charging properties, and residual potential properties of the electrophotographic photosensitive layer are improved. In addition, compounds represented by the general formula (), (), or () have excellent compatibility with various polymeric binders, so even if a large amount of charge transporting substance is contained in the polymeric binder, electrophotographic sensitization is not possible. Since layer turbidity and opacity do not occur, it is possible to widen the range of selection and amount of polymeric binder used for charge transport materials, resulting in favorable charge transport performance and coatings depending on the purpose and application. It is characterized in that an electrophotographic photoreceptor having specific characteristics can be manufactured. The compound represented by the general formula (), () or () has the advantage that it can effectively constitute an electrophotographic photoreceptor even when combined with any charge generating substance. Examples of charge generating substances used in the present invention include the following. (1) Selenium and selenium alloys (2) Inorganic photoconductors such as CdS, CdSe CdSSe ZnO and ZnS (3) Phthalocyanine pigments such as metal and metal-free phthalocyanines (4) Azo dyes such as monoazo and disazo dyes ( 5) Perylene pigments such as perylene anhydride and perylene imide (6) Indigoid dyes (7) Quinacridone pigments (8) Polycyclic quinones such as anthraquinones, pyrenequinones, anthoanthrones and flavanthrones (9) Bisbenzimidazole pigments (10) Cyanine dyes (11) Squarylium derivatives (12) Indanthrone pigments (13) Xanthene dyes (14) Electron-donating substances such as poly-N-vinylcarbazole and trinitrofluorenone, etc. (15) A eutectic complex formed from a pyrylium salt dye and a polycarbonate resin, and (16) amorphous silicon. In the present invention, the polymer binder used with the compound represented by the general formula (), () or () is a hydrophobic, electrically insulating film-forming polymer or copolymer with a high dielectric constant. be. Examples of such high molecular weight polymers or copolymers include the following. (1) Polystyrene resin (2) Polyvinyl chloride resin (3) Polyvinylidene chloride resin (4) Polyvinyl acetate resin (5) Acrylic resin (6) Methacrylic resin (7) Styrene-butadiene copolymer (8) Vinylidene chloride Acrylonitrile copolymer (9) Vinyl chloride-vinyl acetate copolymer (10) Silicone resin (11) Polyester resin (12) Polycarbonate resin (13) Styrene-alkyd resin (14) Silicone-alkyd resin (15) Phenol-formaldehyde Resin These polymeric binders can be used alone or in combination
Although more than one type of polymeric binder can be used as a mixture, the polymeric binder that can be used in the present invention is not limited to these. Furthermore, a plasticizer can also be added together with the binder. Plasticizers include biphenyl, biphenyl chloride, o-terphenyl, p-terphenyl, dibutyl phthalate, dimethyl glycol phthalate, dioctyl phthalate, triphenyl phosphoric acid,
Examples include methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, dilaurylthiodipropionate, 3,5-dinitrosalicylic acid, and various fluorohydrocarbons. A sensitizing agent may also be used in combination with the above-mentioned binder. The sensitizers used include triallylmethane dyes such as Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6B, Rhodamine B, Rhodamine 6G, Rhodamine G Extra, Eosin S, xanthene dyes such as erythrosine, rose bengal, fluorescein, thiazine dyes such as methylene blue, cyanine dyes such as cyanine and 2,6-diphenyl-4-(N·N-dimethylaminophenyl) thiapyrylium perchlorate, Examples include pyrylium dyes such as benzopyrylium salt (described in Japanese Patent Publication No. 48-25658). The photoreceptor of the present invention can be obtained by dispersing or dissolving a charge generating substance together with the charge transporting substance of the present invention in a polymeric binder and providing a uniform layer on a conductive support. However, when an organic dye is used as a charge-generating substance, the organic dye is used in an aggregated state and mixed with a charge-transporting substance in a non-uniform state, resulting in a photoreceptor with high sensitivity and excellent durability. It is preferable in that it is Furthermore, in the photoreceptor of the present invention, a charge generation layer containing a charge-generating substance as a main component is provided on the conductive support via an intermediate layer if necessary, and adjacent to the charge-generating layer, the charge-transporting substance of the present invention is provided as a main component. A photoreceptor having the best electrophotographic properties can be obtained when it has a two-layer structure including a charge transport layer. Furthermore, a photoreceptor obtained by dispersing fine particles of a charge generating substance in a charge transport layer provided on a conductive support via an intermediate layer if necessary can also be effectively used in the present invention. In addition, in the case of a two-layer structure, which of the charge generation layer and the charge transport layer is to be used as the upper layer is determined depending on whether the charging polarity is positive or negative. That is,
In the case of negative charging, it is advantageous in terms of characteristics to use the charge transport layer as the upper layer. In the present invention, the general formula (), () or ()
Since the compound represented by is superior in positive charge transfer, it is advantageous to use the charge transport layer as an upper layer. When the photoreceptor of the present invention has a two-layer structure consisting of a charge generation layer and a charge transport layer, the charge generation layer can be placed directly on the conductive support or, if necessary, with an adhesive layer or barrier layer. (1) vacuum evaporation, (2) apply a solution of a charge generating substance dissolved in a suitable solvent, or (3) apply a charge generating substance to a dispersion medium using a ball mill, homomixer, etc. It can be provided by a method such as applying a dispersion obtained by mixing and dispersing fine particles with a polymeric binder as necessary. The polymer binder used at this time may be the same as that used in the charge transport layer. The charge generation layer constituting the photoreceptor of the present invention can have any thickness, but is 0.05 μm to 5 μm.
The thickness is preferably 0.1 μm to 3 μm, more preferably 0.1 μm to 3 μm. Further, the charge transport layer constituting the photoreceptor of the present invention can have any thickness, but is 5 μm to 30 μm.
m is preferred. When using the compound of the present invention, it is used together with a polymeric binder, and the polymeric binder is preferably used in an amount of 0.8 to 4 parts by weight per 1 part by weight of the compound of the present invention, and the charge generating substance and the charge transporting substance are used in the same layer. When used in the composition, it is preferable to use 0.8 to 4 parts by weight of the polymer binder and 0.1 to 2 parts by weight of the charge generating substance per 1 part by weight of the compound of the present invention. Further, when the charge generation layer is a dispersion system of a charge generation substance and a polymer binder, it is preferable to use the polymer binder in an amount of 10 parts by weight or less per 1 part by weight of the charge generation substance. Other uses of the photoreceptor of the present invention include high resolution and etching after image exposure and toner image formation.
Highly durable, highly sensitive printing plate (lithography or letterpress)
There are industrial advantages such as the ability to obtain The conductive support constituting the photoreceptor of the present invention may be paper or plastic support whose surface is made conductive by applying a conductive compound or a thin metal layer, or if necessary palladium, aluminum, etc. are forged or made. Any material such as a vacuum-deposited metal plate or an aluminum plate can be used. In addition to the above-mentioned polymer binder, materials constituting the intermediate layer that may be provided as necessary include organic polymer compounds such as casein, gelatin, starch, polyvinyl alcohol, polyvinyl acetate, ethyl cellulose, and carboxymethyl cellulose, or oxidized Metal oxides such as aluminum are used. Next, the present invention will be explained in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
In the following examples, all parts indicate parts by weight. Synthesis Examples 1 to 9 Synthesis examples of the compound (13) of the present invention are shown below. o-benzylhydroxylamine hydrochloride 24g
and 28 g of p-dimethylaminobenzophenone were reacted under reflux for 2 hours in a mixed solvent of 300 ml of ethanol and 50 ml of pyridine. water after cooling
200 c.c. was added, and the precipitated solid was collected and washed with water.
By recrystallizing with ethanol solvent, o-benzyl, (p-dimethylamino)benzophenoxime
30g compound (13) I got it. mp122.5℃ Yield 76% Other compounds were similarly synthesized from the corresponding hydroxylamine derivatives and aldehydes or ketones. Examples of the compounds and their melting points are shown below.

【table】

[Table] Example 1 A selenium layer with a thickness of 0.4 μm was provided on the surface of a grained aluminum plate with a thickness of 0.3 mm by vacuum evaporation to serve as a charge generation layer. Compound (8) on this
4.6 parts of polycarbonate and 5.4 parts of bisphenol A
After applying a solution of 78 parts of 1,2-dichloromethane using a wire round rod,
Dry to form a charge transport layer with a thickness of 8 μm.
An electrophotographic photoreceptor having an electrophotographic photosensitive layer consisting of layers was prepared. This photoreceptor was negatively charged by -5KV corona discharge using an electrostatic copying paper tester (manufactured by Kawaguchi Electric Co., Ltd., model SP-428), and then the color temperature was adjusted to 3000〓.
Using a tungsten lamp, we irradiated the surface with light at 4.5 lux, and measured the half-decrease exposure amount E50 (Lux sec) by determining the time required for the surface potential to attenuate to half of the initial surface potential.
It was 11.0 (Lux・sec). After repeating the two steps of charging and exposure 3000 times, the _E50 value hardly changed. Examples 2 to 12 Instead of compound (1), (1), (4), (5),
(6), (9), (12), (13), (14), (15), (18), (
20) A photoreceptor with a two-layer structure was prepared in the same manner as in Example 1, except that the compound represented by (20) was used, and the half-reduction exposure due to negative charging was measured in the same manner as in Example 1.
The following values were obtained.

[Table] Example 13 5 parts of β-type copper phthalocyanine was added to cyclomethane.
After 660 parts of the dispersion was added and subjected to ultrasonic dispersion, 40 parts of bisphenol A polycarbonate and 40 parts of compound (8) were added and dissolved to prepare a coating solution. This coating solution was applied onto a conductive transparent support (a 100 μm polyethylene terephthalate film with a vapor-deposited film of indium oxide on the surface; surface electrical resistance: 10 ³ Ω) using a wire round rod, and dried. An electrophotographic photoreceptor having an electrophotographic photosensitive layer having a thickness of 9.5 μm was prepared. After positively charging this photoreceptor with a +5KV corona discharge, we measured the half-life exposure, and found that E ₅₀ was
It was 13.4 (Lux・sec). Example 14 Two parts of Chlordiane Blue represented by the following structural formula and two parts of polycarbonate of bisphenol A were added to 260 parts of dichloromethane, and the mixture was ground and mixed in a ball mill to prepare a liquid. Using a wire round rod, it is coated on a conductive transparent support (a 100 μm polyethylene terephthalate film with a vapor-deposited film of indium oxide on the surface. Surface resistance: 10 ³ Ω), dried, and a 1 μm thick charge is generated. Created a layer. Next, a solution of 2 parts of compound (19) and 4 parts of polycarbonate of bisphenol A dissolved in 60 parts of dichloromethane was applied onto the charge generation layer using a wire round rod and dried to form a layer with a thickness of about 8 μm. A charge transport layer was formed. Regarding the electrophotographic photoreceptor having the photosensitive layer composed of two layers thus obtained, the half-reduction exposure due to negative charging was measured in the same manner as in Example 1.
_E50 was 16.0 (Lux・sec). Examples 15 to 17 Two-layer photoreceptors were prepared in the same manner as in Example 14, except that the compounds represented by (4), (5), and (8) were used instead of the compounds, respectively. Example 1 and
In the same way, measure the half-decreased exposure due to negative charging,
The following values were obtained.

[Table] Next, embodiments of the present invention are shown. (1) A patent claim having a photosensitive layer containing at least one compound selected from the compounds (), (), and () described in claim 1 and a charge-generating substance. The electrophotographic photoreceptor according to Range 2. (2) The electrophotographic photoreceptor according to embodiment (1), wherein the photosensitive layer contains at least one kind of polymer binder. (3) A charge generating substance is contained in the charge transport layer containing at least one compound selected from the compounds (), (), and () according to claim 1, which is provided on the conductive support. The electrophotographic photoreceptor according to claim 2, comprising a photosensitive layer obtained by dispersing fine particles of. (4) A charge generation layer containing a charge generation substance as a main component on a conductive support and at least one compound selected from the compounds (), (), and () according to claim 1. An electrophotographic photoreceptor comprising charge transport layers provided in this order or in the reverse order. (5) The polymer binder is 0.8% by weight of at least one compound selected from the compounds (), (), and () described in claim 1.
The electrophotographic photoreceptor of embodiment (2) in which the amount is 4 parts by weight. (6) The electrophotographic photoreceptor according to embodiment (4), which uses a conductive support provided with an intermediate layer.

Claims (1)

[Claims] 1. A photoconductive composition containing a compound represented by the general formula (), (), or (). R ¹ represents an alkoxy group, an aralkyloxy group, or a substituted amino group represented by the formula; R ¹⁰ and R ¹¹ are an alkyl group with or without a substituent, or a phenyl group with or without a substituent; R ¹⁰ and R ¹¹ represent a group that can be linked to form a heterocycle containing a nitrogen atom, and R ¹⁰ and R ¹¹ may be the same or different; R ² and R ³ are hydrogen atoms; , represents a halogen atom, an alkyl group or a lower alkoxy group, which may be the same or different types of groups; R ⁴ represents a hydrogen atom, an alkyl group, a phenyl group with or without a substituent; R ⁵ is a hydrogen atom, an alkyl group, an aralkyl group,
Represents a phenyl group with or without a substituent. A has 10 or more carbon atoms with or without a substituent
20 fused carbon rings, monocyclic or fused 5-membered hetero rings represented by the following structural formula, or fused 6-membered hetero rings
Represents a member ring; [formula] [formula] Y and Z are S, O, N-R ⁹ (R ⁹ is 1 carbon number
to 4 alkyl groups) and may be the same or different atoms; R ⁶ and R ⁷ are the same or different groups and represent a hydrogen atom, an alkyl group, or an alkoxy group, or R ⁶ and Represents a group that can be linked with R ⁷ to form a benzene ring or a naphthalene ring; R ⁸ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a monoalkylamino group, a dialkylamino group, an amide group, or a nitro group, which may or may not have a substituent. may be; B represents an arylene group with or without a substituent. 2. An electrophotographic photoreceptor having a photosensitive layer made of a photoconductive composition containing a compound represented by the general formula (), (), or (). R ¹ represents an alkoxy group, an aralkyloxy group, or a substituted amino group represented by the formula; R ¹⁰ and R ¹¹ are an alkyl group with or without a substituent, or a phenyl group with or without a substituent; R ¹⁰ and R ¹¹ represent a group that can be linked to form a heterocycle containing a nitrogen atom, and R ¹⁰ and R ¹¹ may be the same or different; R ² and R ³ are hydrogen atoms; , represents a halogen atom, an alkyl group or a lower alkoxy group, which may be the same or different types of groups; R ⁴ represents a hydrogen atom, an alkyl group, a phenyl group with or without a substituent; R ⁵ is a hydrogen atom, an alkyl group, an aralkyl group,
Represents a phenyl group with or without a substituent. A has 10 or more carbon atoms with or without a substituent
Represents 20 fused carbocycles or a monocyclic or fused 5-membered heterocyclic ring or a fused 6-membered heterocyclic ring represented by the following structural formula; [Formula] [Formula] Y and Z are S, O, N-R ⁹ (R ⁹ is 1 carbon number
to 4 alkyl groups) and may be the same or different atoms; R ⁶ and R ⁷ are the same or different groups and represent a hydrogen atom, an alkyl group, or an alkoxy group, or R ⁶ and Represents a group that can be linked with R ⁷ to form a benzene ring or a naphthalene ring; R ⁸ is a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a monoalkylamino group, a dialkylamino group, an amide group, or a nitro group, which may or may not have a substituent. may be; B represents an arylene group with or without a substituent.