JPS6139050A - Photoconductive film and electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an org. semiconductor film having high sensitivity by contg. oxathiillium salt compd. CONSTITUTION:A titled body is constituted with an electrophotographic sensitive body provided with the photoconductive film contg. the oxathiillium salt compd. expressed by formulas I -III and the photosensitive layer contg. the oxathiillium salt compd. expressed by formulas I -III on a conductive substrate. The film contg. the oxathiillium salt compd. exhibits photoconductivity and can be used for the photosensitive layer of the following electrophotographic sensitive body: More specifically, the film of the oxathiillium salt compd. is formed by a vacuum deposition method on the conductive substrate or said compd. is dispersed and incorporated into a suitable binder, then the film is formed, by which the electrophotographic sensitive body can be prepd. The more preferable embodiment is the application of the photoconductive film as an electric charge generating layer in the electrophotographic sensitive body of which the photosensitive layer is separated in function to the charge generating layer and charge transfer layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel photoconductive coating and a highly sensitive electrophotographic photoreceptor using the same.

BACKGROUND ART Conventionally, pigments and dyes exhibiting photoconductivity have been published in numerous publications.

For example, “RCA Review” Vol. 23
, P., 413-F, 419 (1962, 9), published on the photoconductivity of phthalocyanine pigments, and an electrophotographic photoreceptor using this 7-r:17 anine pigment was published in US Patent No. pJJ3397086. This is disclosed in publications such as US Pat. No. 3,816,118. In addition, examples of organic semiconductors used in electrophotographic photoreceptors include US Pat. No. 4,315,983 and US Pat. No. 4,327.
Publication No. 169 and “Re5aach Disclosure
e”20517 (1981, 5), squaric acid methine dyes shown in U.S. Pat. No. 382.4099, U.S. Pat. No. 3,898,084, and U.S. Pat. No. 4,251,613. Examples include disazo pigments shown in et al.

Such organic semiconductors are easier to synthesize than inorganic semiconductors, and can be synthesized as compounds that have photoconductivity for light in the required wavelength range. An electrophotographic photoreceptor formed on a conductive support has the advantage of improved color sensitivity, but only a few of them are practical in terms of sensitivity and durability.

Problems to be Solved by the Invention The first object of the present invention is to provide a highly sensitive organic semiconductor coating.

A second object of the present invention is to provide an electrophotographic photoreceptor using a photoconductive film made of a highly sensitive organic semiconductor.

A third object of the present invention is to provide an electrophotographic photoreceptor suitable for an electrophotographic copying machine.

Means and Action for Solving the Problems The present invention provides a photoconductive coating containing an oxathiylium salt compound represented by the following general formula (1), (or (6)) and a conductive support. It is composed of an electrophotographic photoreceptor characterized in that it is provided with a photosensitive layer containing an oxatiylium salt compound represented by formula (1), (2), or (3).

General formula (1) In the formula, μ is an integer of 0.1 or 2, or penzoxatii which may have a substituent! Ai is a residue for forming a naphthoxathiilicum ring, and substituents include lower alkyl groups such as methyl, ethyl, propyl, and butyl, and lower alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy. group, halogen atoms such as fluorine, chlorine, bromine, and iodine, and functional groups such as nitro groups. R1 is an aromatic hydrocarbon group derived from benzene, naphthalene, anthracene, helene, fluorene, etc. which may have a substituent, or phenothiazine, phenoxazine, carbazole, indole, hyrol, 7. F-n, thiophene,
Represents a heterocyclic group derived from dibenzofuran, acridine, etc. Substituents include lower alkyl groups such as methyl, ethyl, propyl, butyl, lower alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, aryloxy groups such as phenoxy, and methyl. Alkylmercapto groups such as mercapto and ethylmercapto, amine groups, dialkylamino groups such as dimethylamino, diethylamino, dipropylamino, and dibutylamino, dialkylamino groups such as dibenzylamino, diarylamino groups such as dienylamino, methylphenylamino , alkylaryl amino groups such as ethylphenylamino, cyanethylphenylamino, chloroenalphenylamino, alkylaralkylamino groups such as benzylmethylamino, benzylethylamino, benzyl 7-anoethylamino, acylkylarylamino groups such as benzylphenylamino Examples include cyclic amino groups such as , piperidino, morpholino, and pyrrolidino, I-arylethylene groups such as p-dimethylaminostyryl, and arylazo groups such as p-dimethylaminophenylazo.

8- is an anion group, and specific examples include Ni, B
r-1an-, c1o4-1BP'4-, FB"4-
1HsO0SO5-, 0H5SOs-102H5SO5
Anions such as -, 0H5804- are included.

General formula (2) In the formula, X and A- have the same meaning as X%A- in the general formula (1), R2
, R3 also have the same meaning as R1 in general formula (1), and R2 and R3 may be the same or different.

General formula (3) where m is an integer of 0.1.2 or 6, n is 0 or 1
X is an integer of A- is the same as X and A'' in general formula (1), Y is o, s, sθ or To atom as Y', or N-R4 as Y', However, R4 is an alkyl group such as methyl, ethyl, propyl, butyl,
2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 6-hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-chloropropyl,
Substituted alkyl groups such as 5-f lomopropyl and 6-carboxypropyl, substituted or unsubstituted aralkyl groups such as k-methyl, phenethyl, α-s7tylmethyl, chlorobenzyl, and fromobenzyl, phenyl, tolyl, naphthyl, nitrophenyl, etc. represents a substituted or unsubstituted aryl group, etc. 2 is pyridine, thiazoline, thiazole, benzthiazole, naphthothiazole, oxazoline, oxazole, carrotsoxazole, naphthoxazole, imidacilline, imidazole, inzimidazole, natutoimidazole, benzselenazole, quinoline, inoquinoline, indole, oxadiazole, Thiadiazole, pyrylium, benzpyrylium, naphtopyrylium and heterocycles in which 0 atoms thereof are substituted with 8e and Tθ, and >N-R4 in the ring of benzoxathylium, naphtho, xathylium, pennzdithylium, naphthopyrylium, etc. or 10-, -5-1-8e-1-T
Indicates a residue forming a heterocycle containing e-, and such a heterocycle includes a halogen atom such as fluorine, chlorine, bromine, and iodine, an alkyl group such as methyl, ethyl, propyl, and butyl, methoxy, ethoxy, and propoxy. , an alkoxy group such as butoxy, a nitro group, or an aryl group such as phenyl or tolyl. Substituents for the H atom attached to the C atom in the chain connecting two heterocycles include fluorine,
Halogen atoms such as chlorine, bromine and iodine; cyano groups; alkyl groups such as methyl, ethyl, propyl and butyl; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy;
Examples include alkylmercapto groups such as methylmercapto, ethylmercapto and butylmercapto, and aryl groups such as phenyl.

Next, a general method for producing the oxathiylium salt compound used in the present invention will be described.

The compound represented by the general formula (1) is Reaction formula (1) Reaction formula (2) Reaction formula 〇) (The symbols in each reaction formula have the same meaning as the symbols in General formula (1), and f is 9-1. 0 or 1).

The compound of general formula (2) is generally synthesized according to reaction formula (4) and reaction formula (5) (the symbols in each reaction formula have the same meaning as the symbols in general formula (2)). This method is described in detail in BP 903994.

The compounds of general formula 〇) are Reaction formula (6) Reaction formula (7) Reaction formula (8) Reaction formula (9) Reaction formula (10) Reaction formula (11) -, -2,, i', R30-(4C !HZHjY ) A-Reaction formula (12) Reaction formula (16) It is generally synthesized by the following methods.

(The symbols in the reaction formula have the same meaning as the symbols in general formula (3), and R5 represents the hydrogen atom or its substituent in the chain connecting the two heterocycles.) These compounds correspond to HeI+v can be synthesized according to the oxatiylium salt compound.

ahm, Acta 46, 2167 (1963
) also has iJt[.

Specific examples of the oxathiylium salt compounds used in the present invention are listed below.

Compound point: 10' H, 500 The coating containing the oxathiylium salt compound described above exhibits photoconductivity, and therefore can be used in the photosensitive layer of the electrophotographic photoreceptor described below.

That is, in a specific example of the present invention, an electrophotographic photoreceptor is formed by forming a film of the above-mentioned oxathiylium salt compound on a conductive support by vacuum evaporation, or by dispersing it in a suitable binder and forming a film. It can be prepared.

In a preferred embodiment of the present invention, the photoconductive coating described above can be applied as a charge generation layer in an electrophotographic photoreceptor in which the photosensitive layer is functionally separated into a charge generation layer and a charge transport layer.

The charge generation layer contains as much of the above-mentioned photoconductive compound as possible in order to obtain sufficient absorbance, and is a thin film layer, for example, 5μ or less, in order to shorten the range of the generated charge carriers. Preferably, the thin film layer has a thickness of 0.001 μm. 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 not deactivated by recombination or trapping, but are transferred to the charge transport layer. This is due to the need for injection.

The charge generation layer can be formed by dispersing the above-mentioned compound in a suitable binder and coating it on the substrate, or can be obtained by forming a film deposited in a vacuum deposition apparatus. The binder that can be used when forming the charge generating layer by coating can be selected from a wide range of insulating resins, and can also be selected from organic photoconductive polymers such as poly-H-vinylcarbazole, polyvinylant-2cene, and polyvinylpyrene. .

Preferably, polyvinyl butyral, polyarylate (
Condensation polymers of bisphenol A and 7-talic acid, etc. ) Insulating resins such as polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinylpyridine, cellulose-based AT resin, phrethane resin, epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone can be mentioned. can. 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 charge transport layer or undercoat layer described below. Specific MAIS agents include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, amides such as H,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl Sulfoxides such as sulfoxide, ethers such as tetrahydro7rane, dioxane, ethylene glycol monomethyl ether, esters such as methyl acetate, ethyl acetate, chloroform, methylene chloride,
ZIKU C1# Echin, 4fMr carbonized carbon X s)
Aliphatic halogenated hydrocarbons such as dichloroethylene, 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-Barr coach ink 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, either stationary or under ventilation.

The charge transport layer is electrically connected to the charge generation layer described above, and has the 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. At this time, this charge transport layer may be laminated on or under the charge generation layer. However, if the charge generation layer is the uppermost layer, the coating film may be scratched during repeated use, causing a change in sensitivity.The stain transport layer is preferably laminated on 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" used herein includes a broad definition of "light rays" including r-rays, X-rays, ultraviolet rays, visible light, near-infrared rays, infrared rays, far-infrared rays, and the like. When the photosensitive wavelength range of the charge transport layer coincides with or overlaps that of the charge generation layer, charge carriers generated in both layers trap each other, resulting in a decrease in sensitivity.

Charge-transporting substances include electron-transporting substances and hole-transporting substances, and electron-transporting substances include chloranil, furoanil, tetracyanoethylene, tetracyanoquinodimethane, and 2,4,7-trinitro-9-fluorenone. ,
2,4,5.7-tetranitro-9-fluorenone, 2
, 4.7-trinitro-9-si'/anomethylenefluorenone, 2.4,5.7-titranitroxanthone,
Examples include electron-withdrawing substances such as 2,4,8-tonide-o-thioxanthone, and polymerized versions of these electron-withdrawing substances.

Examples of hole transporting substances include pyrene, N-ethylcarbazole, N-isopropylcarbazole, N-1'thyl-
N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-6-methylidene-9-ethylcarbazole, x,N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine , N,N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, P-diethylaminobenzaldehyde-N,N-diphenylhydrazone, P
-diethylaminobenzaldehyde-N-α-naphthyl-N-7enylhydrazone, P-pyrrolidinobenzaldehyde-N,N-diphenylhydrazone, 1,3.3-
) rifthylindolenine-ω-aldehyde-N,N-
Hydrazones such as diphenylhydrazone, P-u ethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2,5-bis(p++ diethylaminophenyl)-1,3,4-, txadiazole, 1
-Phenyl-3-(P-diethylaminostyryl)-5
-(P-diethylaminophenyl)pyrazoline, 1-[
quinolyl (2) ) -3-(p-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl (2) ) -3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl ) Pyrazoline, 1-[6-medoxypyridyl (2)
] -3-(P-')ethyl-reaminostyl)-
5-(P7diethylaminophenyl)pyrazoline, 1-
[Pyridyl (3)] -3'-(p-diethylaminostyryl)-5-(pu-ethylaminophenyl)pyrazoline, 1-[lepidyl (2))-3-(P-diethylaminostyryl)-s-( p-diethylaminophenyl)pyrazoline, 1-[pyridyl C2))-3-(P-diethylaminostyryl)-4-methyl-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridinobe2
]-s-<α-methyl-P-diethylaminostyryl)
-5-(P-diethylaminophenyl)hilazoline, 1
-7enyl-3-(P-diethylaminostyryl)-4
Pyrazolines such as -methyl-5-(P-diethylaminophenyl)pyrazoline, 1-phenyl-3-(α-benzyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, spiropyrazoline, 2-(P-diethylaminophenyl)pyrazoline, -diethylaminostyryl)-6-ethylamino(zuoxasol, 2-(P-diethylaminophenyl)-4-(P-dimethylaminophenyl)-5
-(2-Qcl phenyl)oxazole and other oxazole compounds, 2-(P-diethylaminostyryl)-
6-:) Thiazole compounds such as ethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N-diethylamine- 2-
polyarylalkane such as methylphenyl)hebutane, 1,1,2,2-tetrakis(4-N,N-dimethylamino-2-methylphenyl)ethane, triphenylamine, poly-N-vinylcarbazole, polyvinyl Examples include pyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, helene-formaldehyde resin, and ethylcarpasol formaldehyde resin.

In addition to these organic charge transport materials, inorganic materials such as selenium, selenium-tellurium amorphous silicon, and cadmium sulfide can also be used.

Further, these charge transport substances can be used alone or in combination of two or more.

When the charge transport material does not have film-forming properties, a film can be formed by selecting an appropriate binder. Examples of resins that can be used as binders include acrylic resin,
polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-styrene copolymer,
Insulating resins such as acrylonitrile-butadiene copolymer, polyvinyl butyral, polyhinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber, and organic photoconductive materials such as poly-N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene. Polymers can be mentioned.

The charge transport layer cannot be made thicker than necessary because there is a limit to how much charge carriers can be transported. Generally, it is 5 to 30μ, but the preferred range is 8 to 20μ.
It is. 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. Examples of substrates having a conductive layer include those in which the substrate itself is conductive;
For example, aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium,
Nickel, indium, gold, platinum, etc. can be used, and plastics (for example, polyethylene , polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin,
(polyfluorinated ethylene, etc.), substrates made by KJHWing conductive particles (e.g. carbon black, silver particles, etc.) on plastic with a suitable binder, substrates made by impregnating plastic or paper with conductive particles, plastics containing conductive polymers, etc. 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 is casein,
Polyhinyl alcohol, nitrocellulose, ethylene-
Acv/L/acid copolymer, polyamide (nylon 6,
It can be formed from nylon 66, nylon 610, copolymerized nylon, 1-rukoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc.

The thickness of the subbing layer is 01 to 5μ, preferably 0.5 to 3μ.
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 is an electron transport material, the surface of the charge transport layer must be positively charged, and exposure after charging is required. Then, in the exposed area, electrons generated in the charge generation layer are injected into the charge transport layer, and then reach the surface and neutralize the positive charges, causing a decrease in surface potential and creating an electrostatic puncture layer between the exposed area and the unexposed area. arise.

A visible image can be obtained by developing the electrostatic latent image thus formed with a negatively charged toner. Either fix this directly or transfer the toner image to paper or plastic film, etc.
It can be developed and fixed.

Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor is transferred onto an insulating layer of transfer paper, then developed and fixed. The type of developer, the developing method, and the fixing method may be any known ones or known methods, and are not limited to specific ones.

On the other hand, when the charge transport material consists of a hole transport material, the surface of the charge transport layer must be negatively charged, 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 charges, resulting in attenuation of the surface potential and an electrostatic contrast between the surface potential and the unexposed area. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transporting substance is used.

Furthermore, it is also possible to form a single-layer type photoreceptor in which an oxatiylium salt compound is dispersed in the binder resin.

Further, in another specific example of the present invention, the above-mentioned human 2 sins,
Organic photoconductive substances such as pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, triphenylamine, polyx-vinylcarbazoles, and inorganic photoconductive substances such as zinc oxide, cadmium sulfide, and selenium. The photosensitive film may contain the above-mentioned oxatiylium salt compound as a sensitizer.

This photosensitive film is formed by coating these photoconductive substances and the above-mentioned oxatiylium salt compound together with a binder.

Further, as another specific example of the present invention, Japanese Patent Application Laid-Open No. 49-9164
It can also be used as a type of photoreceptor in which a charge generating material is dispersed in a charge transfer complex as disclosed in Publication No. 8 (Photoconductive Part #K).

Each photoreceptor contains at least one kind of oxathiylium salt compound selected from the compounds represented by the general formula (1), (2), or (3), and if necessary, other photoconductive materials having different light absorption. By using a combination of pigments and dyes, it is possible to increase the sensitivity of this photoreceptor or to prepare it as a panchromatic photoreceptor.

The electrophotographic photoreceptor of the present invention can be used not only in electrophotographic copying machines but also in a wide range of electrophotographic applications such as laser beam printers, LJCD printers, and CRT printers.

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

Examples 1 to 60 Ammonia aqueous solution of casein (casein 1
1.2 F, 28 thiammonia water (11 ml, water 222 mA)) was applied using a Mayer Parr so that the film thickness after drying was 1.0 μm, and then dried.

Next, butyral resin (butyralization degree 65 mo Al) 2
In a solution dissolved in 95m of f1 inpropyl alcohol,
30 types of oxatiylium salt compounds listed in the table below 5f
t-30 types of coating fluids in addition to each one? il-prepared.

Each coating solution was dispersed in a sand mill for 4 hours, and then coated on the casein subbing layer described above using a Mayer par so that the film thickness after drying was α1μ, and dried to form a charge generation layer. .

Rate resin (number average molecular weight I Oo, 000) 5
f was dissolved in benzene 70-, and this was applied onto the charge generation layer using a Mayer Par so that the film thickness after drying would be 12μ, and dried to form a charge transport layer.

The 25 types of electrophotographic photoreceptors prepared in this way were statically charged with corona at -5 kl' using an electrostatic copying paper testing device Model ISF-428 manufactured by Kawaguchi Denki, and after being held in a dark place for 1 second. , and the charging characteristics f were investigated by exposing to light for 4 seconds at an illuminance of 5 Qug.

The charging characteristics are the initial charging potential (vO) and the amount of lightless light required to attenuate the potential after 1 second of dark decay (]l
C%) was measured. The results are shown in Table 1. or,
The residual potential after 20 flux-eec exposure was expressed in vR.

Table 1 1 610 2.1 02 2
620 Kushi 533 6
05 2.0 04 5630 2
．． 9 s 5 6 590 3.4 06 7
6[)0 2.6 07 8 610 3
．． 0' 08 15 615 2.9 59
14 620 3.1 010 18
630 3.2 011 22 625 2
．． 8 512 '23 590 2.9 5
13 25 580 3.4 014 26
585 3.6 015 27 590
2.3.

16 29 600 3.5 517 32
630 5.4 518 33 610
3, 1 5 Examples itlMflihq(t,@”
Fulla To(-v) E%(Am・5ec)
Vi(-v)19 37 600
2.3 020 38
620 3.0021 59
600 3.5 522
41 605. 2.9 02
3 46 620 3.1
524 47 620
3.4 525 48
610 3.1 026 5
0 580 2.5 1027
51 600 2.4
028 52 610
3.6 029 53600
2.4 030 54
620 3.15 Comparative Examples 1 to 5 Photoreceptors were prepared in exactly the same manner as in Example 1 except that the following comparative compounds were substituted for the oxatiylium salt compound of Example 1, and the characteristics were investigated. The results are shown in Table 2.

1", - now Table 2 1 1 605 5.4
402 2 620
5.6 503 3
590 7.5 354
4 610 &3
305 5 600
10.3 All of the 30 comparative examples have lower sensitivity and larger residual potential than the examples. Furthermore, using the charge measuring device of Example 1, a voltage of 15 KV was applied using a stator method. After corona charging at Narita and dark decay for 1 second, the illuminance was 20 λuX.
The same charging operation was repeated 5000 times, and the changes in the initial charging potential vO and the residual potential VR after no light were examined were examined. The results are shown in Table 3. In addition, Examples 1.13.18, 37.5
The same measurement was also performed on photoreceptor No. 5.

Third narrow example 12 590 5 610 30
Comparative example 1 605 40 690 140
4 (S10 30 700 1
The photoreceptors of Comparative Example 20 all have high initial residual potentials, and correspondingly, the residual potentials during repeated use are extremely high and the residual potentials are pushed up, resulting in high VDs, which poses a serious problem in terms of potential stability in practice. On the other hand, the embodiment according to the present invention has excellent characteristics in both initial sensitivity and residual potential, and its characteristics after repeated use are also extremely stable.

Example 61 Polyester resin (manufactured by Toyobo ■, Byron 200)
5 fl and 1-[virigirou (2)) -3-(4-
H,N-diethylaminostyryl)-5-(4-N,N
-diethylaminophenyl)pyrazoline 52 was dissolved in methyl ethyl ketone 80-, and the aforementioned oxathylium salt compound NT121. After C1 was added and dispersed, the mixture was coated on a polyester film deposited with aluminum and dried to produce a photoreceptor having a photosensitive layer with a dry film thickness of 13/1.

The characteristics of this photoreceptor were measured by the same method as in Example 1, including the initial charging potential (Vo) and the amount of light exposure (8%) required to attenuate the charging potential when dark decaying for 1 second. It was two things below. (However, the charging polarity was set as ■.) Vn: +580V K: 3.5℃uX@8eO Example 62 Poly-N-vinylcarbazole 1f and the aforementioned oxathiylium salt compound Na185sv were added to 1,2-dichloroethane 10F. After that, the mixture was thoroughly stirred. . The coating liquid thus prepared was applied onto a polyethylene terephthalate film on which aluminum was vapor-deposited using a doctor blade so that the dry film thickness was 15 μm.

The charging characteristics of this photoreceptor were measured in the same manner as in Example 1. However, the charging polarity was set to ■. As a result? Shown below.

vQ: +5601 EH: 3.6 l1ux-see Example 33 Actual tMj Example 32 except that the oxathiylium salt compound N1124 was used in place of the oxathiylium salt compound No. 18 used when preparing the electron photoreceptor of Example 62. After preparing a photoreceptor in exactly the same manner as described above, the charging characteristics of this photoreceptor were measured.

The results are shown below. However, the charging polarity was set to ■.

Vo: +590V 8%: 3.31ax・sea Example 64 Fine particle zinc oxide (SazθX2000 manufactured by Sakai Kagaku ■) 10
f1 acrylic resin (Mitsubishi Rayon - Broken Dial L)
R009) 4 t, ) Luene 101 and the above-mentioned oxaltyllium salt compound 6710-'T-mixed thoroughly in a ball mill, and the resulting coating solution was coated with a doctor on an aluminum-deposited volume and tylene 7 tallate film. It was coated with a blade to a dry film thickness of 21 μm and dried to prepare an electrophotographic photoreceptor.

When the spectral sensitivity of this electrophotographic photoreceptor was measured by spectrophotography using electrophotography, it was found that the photoreceptor of this example showed sensitivity on the long wavelength side compared to the zinc oxide coating that did not contain the oxatiylium salt compound mentioned above. It turned out that it has.

Example 35 A polyvinyl alcohol film having a thickness of 1.1 microns was formed on the aluminum surface of an aluminum vapor-deposited polyethylene terephthalate film.

Next, a coating solution containing the same oxathillium chloride metal as in Example 1 was applied onto the polyvinyl alcohol layer formed previously using a Mayer par so that the film thickness after one drying was 0.1μ, and dried. A charge generation layer was formed.

Next, pyrazoline compound 5t of the structural formula and polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthalic acid)
A solution prepared by dissolving 5F in tetrahydro-72-70 was applied onto the charge generation layer so that the film thickness after drying was 10 μm, and dried to form a charge transport layer.

The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in the examples. The results are shown below.

VQ: -600V R3(: 2.Ojluxφsec Example 36 An ammonia aqueous solution of casein was applied onto an aluminum plate having a thickness of 100 μm and dried to form a subbing layer with a thickness of 1.1 μm.

Then, 2,4.7-)linitro9-fluorenone 5
g and poly-N-vinylcarbazole (number average molecular weight 30
0,000) 5M was dissolved in tetrahydrone lamp 0- to form a charge transfer complex. This charge transfer complex compound and the aforementioned oxatiylium salt compound Na50 1F were added to a solution in which polyester resin (Vylon, manufactured by Toyobo Co., Ltd.) 52 was dissolved in tetrahydro 7ran 70- and dispersed. This dispersion was applied onto the undercoat layer so that the film thickness after drying was 12 μm, and dried. The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in Example 1. These results are
It was as follows. However, the charging polarity was set to ■.

VQ: +560V F% 2 3.3jtuc-sea Example 6
7. Form a polyvinyl alcohol film with a thickness of 1.1μ on the aluminum surface of the aluminum vapor-deposited polyethylene terephthalate film.

Next, the dispersion of the oxatiylium salt compound Na53 used in Example 29 and described above was applied onto the previously formed polyvinyl alcohol layer using a Mayer par so that the film thickness after drying would be 0.5μ, and then dried. A charge generation layer was formed.

Next, pyrazoline compound 5f of one structural formula and polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-inophthalic acid)
A solution obtained by dissolving No. 51 in tetrahydrofuran 704 was applied onto the charge generation layer so that the film thickness after drying was 10 μm, and dried to form a charge transport layer.

The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in Example 1. The results of this were as follows.

To: -590V R54: 2.4 ftux-aea Effects of the Invention In addition to the above, the present invention provides a highly sensitive photoconductive coating and realizes a highly sensitive electrophotographic photoreceptor.

Claims (3)

[Claims] (1) A photoconductive coating containing an oxatiylium salt compound represented by the following general formula (1), (2) or (3). General formula (1) In the formula, l is an integer of 0, 1 or 2, X is a benzoxathiylium ring which may have a substituent, a residue for forming a naphthoxathiylium ring, R_1 is, Aromatic hydrocarbon group or heterocyclic group that may have a substituent, A
^- represents an anion group. General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X has the same meaning as X in general formula (1), R_2, R_3
is synonymous with R_1 in general formula (1), however, R_2 and R
_3 may be the same or different, and A^- is general formula (1)
It is synonymous with A^- in the middle. General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, m is an integer of 0, 1, 2, or 3, n is an integer of 0 or 1, and X is X in general formula (1). , Y is an O, S, Se or Fe atom as Y' or >N as Y''
-R_4, where R_4 is a substituted or unsubstituted alkyl group, aralkyl group, or aryl group, and Z is
A residue for forming a 5- to 6-membered heterocycle that may have a substituent, or a 5- to 6-membered heterocycle fused with an aromatic ring such as benzene or naphthalene that may have a substituent. In the expression, hydrogen attached to a carbon atom in a chain connecting two heterocycles may be substituted with a functional group, and A^- has the same meaning as A^- in general formula (1). (2) An electrophotographic photoreceptor comprising a conductive support and a photosensitive layer containing an oxatiylium salt compound represented by the following general formula (1), (2), or (3). General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, l is an integer of 0, 1 or 2, and X is a benzoxathiylium ring or naphthoxathiylium ring which may have a substituent. The residue to form, R_1, is an aromatic hydrocarbon group or a heterocyclic group that may have a substituent, A
^- represents an anion group. General formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X has the same meaning as X in general formula (1), R_2, R_3
is synonymous with R_1 in general formula (1), however, R_2 and R
_3 may be the same or different, and A^- is general formula (1)
It is synonymous with A^- in the middle. General formula (3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, m is an integer of 0, 1, 2, or 3, n is an integer of 0 or 1, and X is X in general formula (1). , Y is an O, S, Se or Te atom as Y' or >N as Y''
-R_4, where R_4 is a substituted or unsubstituted alkyl group, aralkyl group, or aryl group, and Z is
A residue for forming a 5- to 6-membered heterocycle that may have a substituent, or a 5- to 6-membered heterocycle fused with an aromatic ring such as benzene or naphthalene that may have a substituent. In the expression, hydrogen attached to a carbon atom in a chain connecting two heterocycles may be substituted with a functional group, and A^- has the same meaning as A^- in general formula (1). (3) The electrophotographic photoreceptor according to claim 2, wherein the photosensitive layer is formed by sequentially laminating at least a charge generation layer containing an oxatiylium salt compound as described in claim 2 and a charge transport layer. .