JPS59133553A - Photoconductive film and electrophotographic sensitive body using it - Google Patents

Abstract

PURPOSE:To obtain a photoconductive film suitable for an electrophotographic sensitive body having high sensitivity to light in a long wavelength region by incorporating an azulenium salt compd. to a photoconductive film. CONSTITUTION:A photoconductive compd. film contains a compd. represented by the formula shown here in which R1-R7 are each H, halogen, or a monovalent org. residue; R8, R9 are each H, alkyl, alkoxy, aryl or 4-phenyl-1,3-butadienyl or a heterocyclic group each of the latter 3 may be substd. or unsubstd., and R8 and R9 may form an optionally substd. benzene ring; Z is S or O; A is an atomic group necessary to complete an optionally substd. pyran, thiopyran, selenapyran, benzopyran, benzothiopyran, benzoselenapyran, naphthopyran, naphthothiopyran, or naphtselenapyran; X<-> is an anion residue; and n is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photoconductive coating and a highly sensitive electrophotographic photoreceptor using the same. It has been published in literature, etc.

For example, "RCA Review" Vo423. P-
413-P, 419 (1962, 9), the photoconductivity of 7-thalocyanine pigments was announced, and electrophotographic photoreceptors using this phthalocyanine pigment were disclosed in U.S. Pat. No. 3,397,086 and U.S. Pat. No. 3,816,118.
This is shown in the publication number, etc. In addition, examples of organic semiconductors used in electrophotographic photoreceptors include US Pat. No. 431
No. 5983, U.S. Patent No. 4,327,169, etc.
Re5eachDisclosure” 2051
7 (1981, 5), methine squaric acid dyes shown in U.S. Pat. No. 3,824,099, and U.S. Pat. No. 3,89808.
Examples include disazo pigments disclosed in Publication No. 4, US Pat. No. 4,251,613, and the like.

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. In particular, in recent years, development of organic semiconductors having high sensitivity to long wavelength light such as 700 nm or more has become active, which is useful for the development of low-output semiconductor lasers.

However, compounds with large extinction coefficients for long-wavelength light are generally unstable to heat, etc., and have problems such as being easily decomposed by slight increases in temperature. This makes it substantially difficult to manufacture an infrared-sensitive electrophotographic photoreceptor.

Therefore, the first object of the present invention is to provide a novel organic semiconductor.

A second object of the present invention is to provide a novel organic semiconductor coating.

A third object of the present invention is to provide an electrophotographic photoreceptor using a novel organic semiconductor coating.A fourth object of the invention is to provide an electrophotographic photoreceptor suitable for an electrophotographic copying machine. It is about providing.

A fifth object of the present invention is to provide an electrophotographic photoreceptor suitable for a laser beam scanning type electrophotographic printer.

A sixth object of the present invention is to provide an electrophotographic photoreceptor having high sensitivity to light in a long wavelength range.

This object of the present invention is achieved by an azulenium salt compound represented by the following general formula (1). In the general formula (1), R and -R7 are hydrogen atoms, halogen atoms (chlorine atoms, bromine atoms). , iodine atom) or a monovalent organic residue. Monovalent organic residues can be selected from a wide variety of groups, but especially alkyl groups (methyl, ethyl, n-propyl, inpropyl, n-butyl, t-
Butyl, n-amyl, n-hexyl, n-octyl, 2
-ethylhexyl, t-octyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.)
, substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-su7tyl, β-naphthyl, etc.), substituted or unsubstituted Aralkyl group (benzyl, 2
-phenylethyl, 2-phenyl-1-methylethyl,
Bromobenzyl, 2-bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, trioyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amine groups (amine , dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), Nitro group, hydroxy group, carboxyl group,
Examples include a cyan group or a substituted or unsubstituted arylazo group (enylazo, β-naphthylazo, β-naphthylazo, diethylaminophenylazo, chlorophenylazo, nitronenylazo, methoxystyrylazo, tolylazo, etc.). Also, R1 and R2, R1 and R4
, R4 and R5, R3 and R6, and Ro and R7, substituted or unsubstituted aromatic rings (benzene, naphthalene, chlorobenzene, bromobenzene, methylbenzene, ethylbenzene, methoxybenzene, ethoxybenzene) etc.) may be formed.

R8 and Ro represent a hydrogen atom, an alkyl group (methyl, ethyl, n-propyl, inpropyl, n-butyl, t-
Butyl, n-amyl, n-hexyl, n-octyl, 2
-ethylhexyl, t-octyl, nonyl, dodecyl, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, ethylphenylmethoxyphenyl) , chlorophenyl, =) o phenyl, dimethylaminophenyl, dibenzylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted styryl group, or 4-
Phenyl-1,3-7'tadienyl group (styryl, methoxystyryl, dimethoxystyryl, ethoxystyryl, jetoxystyryl, dimethylaminostyryl, diethylaminosteryl, 4-phenyl-1,3-butadienyl, 4-(p-dimethyl aminophenyl)-1,3-
Butadienyl, 4-(p-diethylaminophenyl)=
1.3-butadienyl etc. ) or a substituted or unsubstituted heterocyclic group (3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, 9-carbazolyl, etc.), and R8 and R are combined and substituted Alternatively, an unsubstituted benzene ring may be formed.

2 represents a sulfur atom, an oxygen atom, or a selenium atom.

A indicates an atom necessary to complete biran, thiobilane, selenaviran, bensohyran, benzothiopyran, benzose L/f pyran, naphthopyran, naphthothiopyran or naphthoselenapyran. These rings contain argyl groups (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-acyl, t-acyl,
n-hexyl, n-octyl, t-octyl, 2-ethylhexyl), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, biphenyl,
Ethylphenyl, methoxyphenyl, ethoxyphenyl, jetoxyphenyl, hydroxyphenyl, chlorophenyl, dichlorophenyl, bromophenyl, cyfromophenyl, nitrophenyl, diethylaminophenyl,
dimethylaminophenyl, dibenzylaminophenylnato), styryl, 4-phenyl-1,3-phtajenyl, methoxystyryl, dimethoxystyryl, ethoxystyryl, jetoxystyryl, dimethylaminostyryl, 4-(p-dimethylaminophenyl)- 1,,3-butadienyl, 4-(p-diethylaminophenyl)-1
, 3-butadienyl and other styryl groups, or 4-phenyl-1,3-butadienyl or its substituted derivatives, or heterocycles such as 3-carbazolyl, 9-methyl-3-carbazolyl, 9-ethyl-3-carbazolyl, and 9-carbazolyl. can be substituted by groups.

■　　　.

x'-' represents an anionic residue such as ha chlorate, picrate, fluorobore 1', p-1 luenesulfonate, bar iodide, chloride, bromide or iodide. n is 0 or 1.

Representative examples of the compound represented by the general formula (1) are as follows.

The azulenium salt compound of the present invention includes a formyl azulene compound represented by the following general formula (2), and a formyl azulene compound represented by the general formula (2) (wherein R1 to R? mean the same as defined above). ) R, R with the compound represented by the general formula (3).

(In the formula, Rs , Re , As Z , X and n have the same meanings as defined above.) It can be easily obtained by reacting in a solvent. A wide range of organic solvents can be used as the solvent, but in particular alcohols such as ethanol, propatool and butanol, nitriles such as acetonetrile, ketones such as methyl ethyl ketone, nitro compounds such as nitrobenzene, and tetrahydrol. Halogenated hydrocarbons such as chloroethane, organic acids such as acetic acid, acid anhydrides such as acetic anhydride, etc. are used.Next, synthesis methods for typical azulenium salt compounds of the present invention will be shown.

Synthesis example 1. : Compound base (2) Three [in one flask, 3. (Ig, 4-methyl-2,6-cyphenylpyrylium verchlorate 4,6
g and 100 ml of acetic anhydride, heated and stirred,
The reaction was carried out at 0 to 90°C for 20 minutes. After cooling, the precipitated crystals were separated and washed with 50 mt of glacial acetic acid.
After sequentially washing twice with 600 ml of water and 25 ml of ethanol (1 m/=) and drying, 687 g of an azulenium salt compound was obtained.

Yield: 91% Decomposition point: 260°C or higher Solution absorption spectrum: λmax 6 in dichloromethane
86 nrn Elemental analysis: Molecular formula CuHsICIOs Calculated value (CuHsICIOs
Analysis value (@ C'73.56 73.43 H5,645,80 C/!, 6,39 6.45 Synthesis example 2.
: Compound A (7) 1-7 ormylu-3,8-dimethyl- in a three-way flask
3.0 g of 5-improlazulene, 4.8 g of 2-merityl-4,6-cyphenylthiobi-containing umperchloride) and 10 (l ml) of acetic anhydride were prepared.
The mixture was heated and stirred and reacted at 90 to 105°C for 40 minutes. After cooling, the precipitated crystals were separated from each other and poured with 50 rnL of rice vinegar.
Wash with 500 ml of water and 25 ml of ethanol.
After sequentially washing twice with 0 mL, the mixture was dried and boiled to obtain 7.0 g of an azulenium salt compound.

Yield: 93% Decomposition point = 240-242°C Solution absorption spectrum: λ+nax in dichloromethane
743 nm Elemental analysis: Molecular formula C34Hs+ ClO4S calculation value book) Analysis value (@ C71,4971,36 H5,485,54 CI 6.21. 6.29 The coating with the azulenium salt compound described above exhibits photoconductivity and therefore It 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 azulenium salt compound on a conductive support by vacuum evaporation, or by forming a film by dispersing the azulenium salt compound in a suitable binder. 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, 5 microns or less, in order to shorten the range of the generated charge carriers. , preferably 0.01 micron to 1
A thin film layer having a thickness of microns is preferable. 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.

The binder that can be used when forming the charge generation layer by coating can be selected from a wide range of insulating resins, and organic photopolymer polymers such as vinylcarbazole, polyvinyl anthracene, and polyvinylpyrene can be used as binders. You can choose from.

Preferably, polyvinyl butyral, polyarylate (
Condensation polymers of bisphenol A and phthalic acid, etc. ) Insulating resins such as polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane 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 it is preferable to select a solvent that does not dissolve the charge transport layer or undercoat layer described below. Specific organic solvents include alcohols such as methanol, 139 ethanol, isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide, N,N
- Amides such as dimethylacetamide, sulfoxides such as dimethylphorphogide, tetrahydrofuran,
Ethers such as dioxane and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichlorethylene, benzene, toluene, Xylene, ligroin, monochlorobenzene, cyclobenzene nanoaromatics, 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. Drying: A preferred method is to dry to the touch at room temperature, followed by heat drying. Heat drying can be carried out at a temperature of 30° to 20° C. for a period of 5 minutes to 2 hours, either stationary or under ventilation.

The charge transport layer is electrically connected to the aforementioned charge generation layer 1-, and receives and takes away the +1 charge carrier injected from the Tllr generation layer in the presence of an electric field, and VC1 carries these charge carriers. In this case, the charge transport layer 1, which has the function of transporting the charge by surface separation, may be laminated on or under the charge generation layer. However, it is desirable that the charge transport layer is laminated on the charge generation layer.

It is preferable that the material that transports the charge gear in the charge transport layer (hereinafter simply referred to as charge transport material) is substantially insensitive to the wavelength range of electromagnetic waves to which the charge generation layer is sensitive. The electromagnetic waves 1 referred to here include γ-rays, X-rays,
It includes the definition of ``a single ray of light'' in a broad sense that includes ultraviolet rays, visible light, near-infrared rays, infrared rays, far-infrared rays, etc. When the photosensitive wavelength range of the charge transport layer coincides with that of the charge generation layer, charge carriers generated in both layers capture 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, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4.7-dolinitro-9-fluorenone,
2.4.5.7-tetranitro-9-fluorenone, 2
．． 4.7-dolinitro9-zineanomethylenefluorenone, 2,4.5.7-titranitroxanthone,2.
There are electron-withdrawing substances such as 4.8-trinidrothioxanthone, and polymerization of these electron-withdrawing substances.

Examples of hole-transporting substances include pyrene, N-ethylcarbazole, N-1 soprovircarbazole, N-methyl-N
-Phenylhydrazino-3-methylythene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylythene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine, N , N-diphenylhydrazino-3-methylidene-10-ethylphenothiazine, P-diethylaminobenzaldehyde-N, N-diphenylhydrazone, P-
Diethylaminobenzaldehyde-N-α-naphthyl-
N-phenylhydrazone, P-pyrrolidinobenzaldehyde-N, N-diphenylhydrazone, 1.3.3-trimethylindolenine-ω-aldehyde)”-N, N-
Hydrazones such as diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone, 2,5-bis(P-diethylaminophenyl)-1,3,4-oxadiazole, 1-phenyl- 3-(P-diethylaminosteryl)-5-(P-
diethylaminophenyl)pyrazoline, 1-(quinolyl(2))-3-(P-diethylaminostyryl)-
5-(P-diethylaminophenyl)vira/IJn,
1-[pyridyl (2)) -3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-(6-medoxypyridyl (2)) -
3-(P-diethylaminostyryl) -5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(
3):] -3-(P-diethylaminostyryl)-
5-(P-diethylaminophenyl)pyrazoline, ■-
(Lepidyl (2)) -3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)hilazoline, 1-[Pyridyl (2)) -3-(P-diethylaminostyryl)-4-methyl-5- CP-diethylaminophenyl)pyrazoline, 1-[pyridyl (2)
]-3-(α-Methyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl) Hirazoline,
1-phenyl-3-(P-diethylaminostyryl)-
Pyrazolines such as 4-methyl-5-(P-diethylaminophenyl)pyrazoline, 1-phenyl-3-(α-benzyl-P-diethylaminostyryl)-5-(P-cyctylaminophenyl)pyrazoline, and subirovirazoline], +'j, 2-(P-diethylaminostyryl)-
Oxazole compounds such as 6-dinithylaminobenzoxazole, 2-(P-diethylaminophenyl)-4-(P-dimethylaminophenyl)-5-(2-10lophenyl)oxazole, 2-(P-diethylaminostyryl) )-thiazole compounds such as 6-dinithylaminopenzothiazole, bis(4-diefruami/-
Triarylmethane compounds such as 2-methylphenyl)-phenylmethane, 1.1-bis(4-N,N-diethylamino-2-methylphenyl)hebutane, 1. , 1.
2.2-tetrakis(4-N,N-dimethylamino-2
- Polyarylalkanes such as methylphenyl)ethane, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, hy1/-formaldehyde resin, ethylcarbazole Formaldehyde resin etc.

In addition to these organic I4F transport materials, inorganic materials such as selenium, selenium-tellurium, amorphous silicon, and cadmium sulfide can also be used. , 1''1i or a combination of two or more types can be used.

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-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone,
Examples include insulating resins such as polyacrylamide, polyamide, and chlorinated rubber, and organic photoconductive polymers such as boryl N-vinylcarbazole, polyvinylanthracene, and polyvinylpyrene.

Since the charge transport layer has a limit in its ability to transport charge carriers, it cannot be made thicker than necessary. Typically it is 5 microns to 30 microns, with a preferred range of 8 microns to 20 microns. When forming the electrolyte layer by coating, an appropriate coating method such as that described in 611 can be used.

A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport J- is provided on a substrate having a conductive layer. As the substrate having a conductive layer, the substrate itself has 4m properties, such as aluminum, aluminum alloy, copper, zinc,
Stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, platinum, etc. can be used, and in addition, aluminum, aluminum alloy, indium oxide, tin oxide, indium oxide-tin oxide alloy, etc. can be coated by vacuum evaporation method. A plastic having a formed layer (e.g. polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, polyfluoroethylene, etc.), conductive particles (e.g. carbon black, silver particles, etc.) are added to the plastic with a suitable binder. A substrate coated with conductive particles, a substrate made of plastic or paper impregnated with conductive particles, a plastic containing a conductive polymer, 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 F side layer is formed from casein, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide (nylon 6, nylon 66, nylon 610, copolymerized nylon, alkoxymethylated nylon, etc.), polyurethane, gelatin, aluminum oxide, etc. can.

The thickness of the undercoat layer is suitably 0.1 micron to 5 micron, preferably 0.5 micron to 3 micron.

When using a photoreceptor laminated with a conductive layer, a charge generation layer, and a charge transport layer IIIM, when the charge transport material is composed of a charge transport material, the surface of the charge transport layer must be positively charged. When post-exposure is performed, 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 1, S, resulting in attenuation of the surface G'j and the unexposed area. An electrostatic contrast occurs between the two.

A visible image is obtained by developing the static fit latent image thus formed with a loaded toner. This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc., then developed and fixed.

Alternatively, a method may be used in which the electrostatic charge on the photoreceptor is transferred to 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 14°C cargo transport substance is composed of a hole transport substance,
It is necessary to charge the surface of the charge transport layer negatively, and when it is exposed to light after being charged, the holes generated in the charge generation layer are injected into the charge transport layer in the exposed area, and then light reaches nti VC and the negative charges are transferred to the inside (1 However, the surface potential attenuates and electrostatic contrast occurs between the toner and the unexposed area.At the time of development, it is necessary to use a positively charged toner, contrary to the case where an electron transport material is used.

In another embodiment of the present invention, the aforementioned hydrazones,
Organic photoconductive substances such as pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, triphenylamine, and hol-1J-N-vinylcarbazoles, and inorganic photoconductive substances such as salivary lead oxide, cadmium sulfide, and selenium. A photosensitive film may be prepared containing the above-mentioned compound as a sensitizer for the 'rlt substance. This photosensitive film is formed by coating these photoconductive substances and the above-mentioned compound together with a binder.

All of the photoreceptors contain at least if*sx azulenium salts selected from the compounds represented by the general formula (1), and are used in combination with other photoconductive pigments or dyes with different light absorptions as necessary. By doing so, it is possible to increase the sensitivity of this photoreceptor or to prepare it as a panchromatic photoreceptor.

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

Examples 1 to 11 Ammonia aqueous solution of casein (casein 1
1.2r of 28% ammonia water, 222md of water) was applied using a Mayer bar so that the film thickness of the dried product was 1.0 micron, and dried.

Next, butyral resin (butyralization degree 63 mol%) 2
To a solution dissolved in 95 liters of inpropyl alcohol, 11 types of azulenium salts listed in the table below were added at intervals, and 1. II was invaded.

After each coating liquid was dispersed with an attritor, it was applied onto the casein undercoat layer described above using a Meyer bar using a punch so that the film thickness after drying was 0.1 micron, and dried to form a charge generation layer. Sase/ko.

hydrazone compound 52 and polymethyl methacrylate resin (number average molecular weight 100,000) 5 f were dissolved in 70 ml of benzene, and this was spread over the charge generation layer using a Mayer bar so that the dry film thickness was 12 microns. Apply,
It was dried to form a charge transport layer.

The 11 electrophotographic photoreceptors prepared in this manner were statically charged with corona at 15 KV using Kawaguchi Electric's Seiden Copying Paper Testing Equipment Model SP-428e, held in a dark place for 10 seconds, and then charged at an illuminance of 5 lux. The charging characteristics were investigated by exposing the sample to light.

As for the charging characteristics, the initial charging potential (VO) and the exposure amount (El/2) required to attenuate the potential to 1/2 after dark decaying for 10 seconds were measured. The results are shown in Table 1. Further, the charge retention rate when dark decayed for 10 seconds was expressed as Vk (%).

1st Table 1 (1,) 520 89 10.52
(2) 58t) 76 19.03 (3)
535 84 11.44 (4>54f
) 88 10°45, (6) 600 70
24.06 (7) 500 90 12.5
7 (8) 540 85 14.68 (
(3) 570 87 18.69 (10)
490 84 9.510 (11) 510
80 10.511 (12) 480 85 1
1. ．． 8 Example 12 Polyester resin (manufactured by Toyobo Co., Ltd., Byron 200) 5
9]-[Viridy-C2))-3-(4-N,N-diethylaminostyryl)-s-(4-N,N-diethylaminophenyl)pyrazoline 5y was dissolved in 80 ml of methyl ethyl ketone, and then the azulenium salt described above was dissolved. Compounds A(7), i, and Oj' were added and dispersed (17), and then 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 microns (1-).

The characteristics of this photoreceptor were determined by the same method as in Example 1: the initial charging potential (vo), the charge retention rate (Vk) when dark decayed for 10 seconds, and the charging potential decayed to 172 when dark decayed for 10 seconds. The exposure amount (El/2) required for this was measured and was as follows.

Vo: -510 volts Vk: 80 gl/2: 34/ux-sec Example 13 Poly-N-vinylcarbazole 1r and the aforementioned azulenium salt compound & (2) 5 mf were added to 10f of 1,2-dichloroethane. After that, stir thoroughly 1. Ta.

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 microns.

The charging characteristics of this photoreceptor were measured in the same manner as in Example 1. However, the charging polarity was set to ■. The results are shown below.

vo: +490 volts Vk: 84% E1/2: 36.81ux-see Example 14 The azulenium salt described above was used in place of the 9 azulenium salt compound &(2) used when preparing the electrophotographic photoreceptor of Example 13. A photoreceptor was prepared in exactly the same manner as in Example 13, except that Compound A(5) was used, and the charging characteristics of this photoreceptor were measured.

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

Vo S +410 volts ■: 79% E1/2: 32.0lux-1, QC Example 15 Fine particle zinc oxide (5Bzex 2000 manufactured by Sakai Chemical ■)
102, acrylic resin (Dyanal LR009 manufactured by Mitsubishi Rayon ■) 49, toluene 102, and the above-mentioned azulenium salt compound A(1)lQ mf were thoroughly mixed in a ball mill, and the resulting coating liquid was mixed with aluminum. An electrophotographic photoreceptor was prepared by coating the vapor-deposited polyethylene terephthalate film with a doctor blade to a dry film thickness of 21 microns and drying.

When the spectral sensitivity of this electrophotographic photoreceptor was measured using spectrophotographs using electrophotography, it was found that the photoreceptor of this example was more sensitive to long wavelengths than the aforementioned zinc oxide coating that did not contain an azulenium salt compound. It was found that it has sensitivity.

[Brief explanation of drawings]

Figures 1 and 2 show Compound A (2) and Compound A
FIG. 3 is an explanatory diagram showing a visible-infrared absorption spectrum of (7) in a dichloromethane solution. Patent applicant Gyanon Co., Ltd.

Claims (2)

[Claims] (1) A photoconductive film characterized by containing a compound represented by the following general formula (1). General formula (1) (wherein, RI%Rt, R,s, R4, Rs, Ra
and R7 represents a hydrogen atom, a halogen atom, or a monovalent organic residue, and Ro and R2, R, and R,, R4 and R3
, R3 and Ro, and R6 and R7, at least one combination may form a substituted or unsubstituted aromatic ring. R8 and Ro are hydrogen atoms, alkyl groups,
Alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted styryl group, substituted or unsubstituted 4
-Phenyl-1,3-phtacy: represents an r-nyl group or a t-substituted or unsubstituted heterocyclic group. Furthermore, R6 and R9 may form a substituted or unsubstituted benzene ring. 2 represents a sulfur atom, an oxygen atom or a selenium atom. A represents an atomic group necessary to complete pyran, thiopyran, selenapyran, benzobylane, benzothiopyran, benzoselenaviran, naphthopyran, naphthothiopyran or naphthoselenabiran, which may be substituted. θX represents an anion residue. n is O or 1. ) (2) An electrophotographic photoreceptor comprising a photosensitive layer containing a compound represented by the following general formula (1) on a conductive support. General formula (1) (wherein R,, R2, R3, R,, R,, Ra and R
7 represents a hydrogen atom, a halogen atom, or a monovalent organic residue, and at least one of the combinations of R8 and R2, R8 and R4, R4 and R3, R6 and Ro, and R6 and R7
A substituted or unsubstituted aromatic ring may be formed by a combination of the two. R8 and Ro are a hydrogen atom, an alkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted styryl group, a substituted or unsubstituted 4-phenyl-1,3-butadienyl group, or a substituted or unsubstituted represents a heterocyclic group. Furthermore, R8 and Ro may form a substituted or unsubstituted benzene ring. 2 represents a sulfur atom, an oxygen atom or a selenium atom. A represents an atomic group necessary to complete the optionally substituted pyran, thiopyran, selenapyran, benzopyran, benzothiopyran, benzoselenapyran, naphthopyran, naphthothiopyran or naphthoselenapyran. θ X does not represent an anionic residue. n is 0 or 1. )