JPH0359427B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel photoconductive coating and a highly sensitive electrophotographic photoreceptor using the same. Conventionally, pigments and dyes exhibiting photoconductivity have been published in numerous publications. For example, “RCA Review” (RCA
Review) Vol. 23, P. 413-P. 419 (September 1962), there was a presentation on the photoconductivity of phthalocyanine pigments, and an electrophotographic photoreceptor using this phthalocyanine pigment was published in U.S. Patent No. 3,397,086. This is disclosed in US Pat. No. 3,816,118, etc. Other organic semiconductors used in electrophotographic photoreceptors include, for example, U.S. Patent No. 4,315,983, U.S. Pat.
The pyrium-based dye shown in U.S. Patent No.
Examples include methine squaritate dyes shown in US Pat. No. 3,824,099, and disazo pigments shown in US Pat. No. 3,898,084 and US Pat. No. 4,251,613. 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. Electrophotographic photoreceptors in which a film is formed on a conductive support have 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, with the development of low-power semiconductor lasers, the development of organic semiconductors with high sensitivity to long-wavelength light such as 700 nm or more has become active. A compound with
In general, it is often unstable to heat, etc., and has problems such as being easily decomposed by a slight rise in temperature. It is difficult to do so. 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 present invention is to provide an electrophotographic photoreceptor suitable for electrophotographic copying machines. 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. Such an object of the present invention is the following general formula [],
This is achieved by an azulenium chloride compound represented by [ ] or [ ]. general formula In the general formulas [], [] and [],
R ₁ to _{R 5} are hydrogen atoms, halogen atoms (chlorine atoms,
bromine atom, iodine atom) or a monovalent organic residue, and X is a substituted or unsubstituted 5-, 6-, or 7-membered
Represents a group of atoms necessary to form a member aromatic ring. Monovalent organic residues can be selected from a wide variety of groups, but especially alkyl groups (methyl, ethyl, n-propyl, isopropyl, 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, ethyl phenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl,
Dimethylaminophenyl. α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted heterocyclic groups (pyridyl, quinolyl, carbazolyl, furyl,
thienyl, pyrazolyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, promobenzyl, 2-promophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, triooyl, naphthoyl,
phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino, diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl) , methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro group, hydroxy group, mercapto group, thioether group, carboxyl group, carboxylic acid ester, carboxylic acid amide, cyano group, unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.). Also, an aromatic ring formed by R ₁ and X, a combination of an aromatic ring formed by X and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₄ and R ₅ At least one combination of substituted or unsubstituted aromatic rings (benzene, naphthalene,
chlorobenzene, ethylbenzene, methoxybenzene, etc.), heterocycles (furan, benzofuran, pyrrole, thiophene, pyridine, quinoline, etc.)
Alternatively, a ring may be formed by an aliphatic chain (dimethylene, trimethylene, tetramethylene, etc.). A
represents a divalent organic residue linked by a double bond. Specific examples of the present invention containing such A are those represented by the following general formulas (1) to (11). However, Q in the formula represents the azulenium skeleton shown below, and the right side excluding Q in the formula represents A. Azulenium skeleton (Q) general formula In the formula, R ₁ to R ₅ and X have the same definitions as defined above. In the formula, R ₁ to R ₅ and X have the same definitions as defined above. In the formula, R' ₁ to R' ₅ represent a hydrogen atom, a halogen atom (chlorine atom, bromine atom, iodine atom) or a monovalent organic residue, and X' is a substituted or unsubstituted 5
6-membered, 6-membered or 7-membered aromatic ring. Monovalent organic residues can be selected from a wide range of options, but especially alkyl groups (methyl, ethyl,
n-propyl, isopropyl, 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, ethyl phenyl, methoxy phenyl, ethoxy phenyl,
chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.),
Substituted or unsubstituted heterocyclic groups (pyridyl, quinolyl, carbazolyl, furyl, thienyl, pyrazolyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-methylethyl, promobenzyl, 2 -promophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl groups (acetyl, propionyl, butyryl, valeryl, benzoyl, triooyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino) , diethylamino, dipropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl, dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.), nitro group, hydroxy group, mercapto group,
Thioether group, carboxyl group, carboxylic acid ester, carboxylic acid amide, cyano group, substituted or unsubstituted arylazo group (phenylazo, α
-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenylazo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.). Also, the aromatic ring of R′ ₁ and X′, the aromatic ring of X′ and R′ ₂ , R′ ₂ and R′ ₃ , R′ ₃ and R′ ₄
,
and aromatic rings (benzene _{, naphthalene} , chlorobenzene, ethylbenzene, methoxybenzene, etc.), heterocycles (furan,
benzofuran, pyrrole, thiophene, pyridine, quinoline, etc.) or aliphatic chains (dimethylene,
(trimethylene, tetramethylene, etc.) may form a ring. Further, the azulenium skeleton represented by Q may be symmetrical or asymmetrical. Z is
Represents an anionic residue. R ₆ is a hydrogen atom, a nitro group, a cyano group, an alkyl group (methyl, ethyl,
propyl, butyl, etc.) or an aryl group (phenyl, tolyl, xylyl, etc.), where n is 0,
Represents 1 or 2. In the formula, R ₁ to R ₅ , X and Z have the same definitions as defined above. In the formula, _R1 to R5, X and Z have the same definitions as defined above. R″ ₁ to R″ ₆ represent a hydrogen atom, a halogen atom (chlorine atom, bromine atom, 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, isopropyl, 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, ethyl phenyl,
methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl, dimethylaminophenyl, α-naphthyl, β-naphthyl, etc.), substituted or unsubstituted heterocyclic groups (pyridyl, quinolyl,
carbazolyl, furyl, thienyl, pyrazolyl, etc.), substituted or unsubstituted aralkyl groups (benzyl, 2-phenylethyl, 2-phenyl-1-
Methyl ethyl, bromobenzyl, 2-bromophenylethyl, methylbenzyl, methoxybenzyl, nitrobenzyl), acyl group (acetyl,
propionyl, butyryl, valeryl, benzoyl, triooyl, naphthoyl, phthaloyl, furoyl, etc.), substituted or unsubstituted amino groups (amino, dimethylamino, diethylamino, dibropylamino, acetylamino, benzoylamino, etc.), substituted or unsubstituted styryl groups (styryl ,
dimethylaminostyryl, diethylaminostyryl, dipropylaminostyryl, methoxystyryl, ethoxystyryl, methylstyryl, etc.),
Nitro group, hydroxy group, mercapto group, thioether group, carboxyl, carboxylic acid ester, carboxylic acid amide, cyano group, substituted or unsubstituted arylazo group (phenylazo, α-naphthylazo, β-naphthylazo, dimethylaminophenylazo, chlorophenyl) azo, nitrophenylazo, methoxyphenylazo, tolylazo, etc.). Also, R″ ₂ and R″ ₃ , R″ ₃ and
Among the combinations of R″ ₄ , R″ ₄ and R″ ₅ , and R″ ₅ and R″ ₆ ,
At least one combination of substituted or unsubstituted aromatic rings (benzene, naphthalene, chlorobenzene, ethylbenzene, methoxybenzene, etc.);
A ring may be formed by a heterocycle (furan, benzofuran, pyrrole, thiophene, pyridine, quinoline, etc.) or an aliphatic chain (dimethylene, trimethylene, tetramethylene, etc.). In the _formula ,
- Represents a group of nonmetallic atoms necessary to complete a nitrogen-containing heterocycle such as quinoline, isoquinoline, or indole; such a heterocycle includes halogen atoms (chlorine, bromine, iodine), alkyl groups (methyl,
(ethyl, propyl, butyl, etc.), aryl groups (phenyl, tolyl, xylyl, etc.), and the like. R ₇ is an alkyl group (methyl,
ethyl, propyl, butyl), substituted alkyl groups (2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-chloropropyl, 3-promo) propyl,
3-carboxypropyl, etc.), cyclic alkyl groups (cyclohexyl, cyclopropyl), allyl, aralkyl groups (benzyl, 2-phenylethyl, 3-carboxypropyl, etc.)
-Phenylpropyl, 4-phenylbutyl, α-
naphthylmethyl, β-naphthylmethyl), substituted aralkyl groups (methylbenzyl, ethylbenzyl,
dimethylbenzyl, trimethylbenzyl, chlorobenzyl, bromobenzyl, etc.), aryl groups (phenyl, tolyl, xylyl, α-naphthyl,
β-naphthyl) or substituted aryl groups (chlorophenyl, dichlorophenyl, trichlorophenyl,
ethyl phenyl, methoxyphenyl, dimethoxyphenyl, aminophenyl, nitrophenyl, hydroxyphenyl, etc.). m represents 0 or 1 and Z has the same definition as defined above. (7) Q = CH-R ₈ Z In the formula, R ₈ is a substituted or unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, α-naphthyl, β-naphthyl, anthralyl, pyrenyl, methoxyphenyl, dimethoxyphenyl) enyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, chlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, ethyl phenyl, diethylphenyl, nitrophenyl, aminophenyl, dimethylaminophenine, diethylaminofenyl enyl, dibenzylaminophenyldipropylaminophenyl, morpholinophenyl, piperidinyl phenyl, piperazinophenyl, diphenylaminophenyl, acetylaminophenyl, benzoylaminophenyl, acetylphenyl, benzoylphenyl , cyanophenyl, etc.), and Z has the same definition as defined above. (8) Q = CH-R ₉ Z where R ₉ represents a monovalent heterocyclic group derived from a heterocycle such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine, pyridine, etc. Z has the same definition as defined above. (9) In the formula, R ₁₀ is a hydrogen atom, an alkyl group (methyl,
ethyl, propyl, butyl) or substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, biphenyl, ethyl phenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, α-naphthyl, β - Naphthyl, anthralyl, pyrenyl, etc.). _R8 and Z
has the same definition as defined above. (10) Q = CH-C≡C-R ₈ where R ₈ and Z have the same definitions as defined above. In the formula, X ₂ represents an atomic group necessary to complete pyran, thiapyran, selenapyran, benzopyran, benzothiapyran, benzoselenapyran, naphthopyran, naphthothiapyran or naphthoselenapyran, which may be substituted. l is 0 or 1. Y represents a sulfur atom, an oxygen atom or a selenium atom. R ₁₁ and R ₁₂ are hydrogen atoms, alkyl groups (methyl, ethyl, propyl, butyl, etc.),
Alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), substituted or unsubstituted aryl groups (phenyl, tolyl, xylyl, chlorophenyl, biphenyl, methoxyphenyl, etc.),
Substituted or unsubstituted styryl group (styryl, p
-methylstyryl, o-chlorostyryl, p-methoxystyryl, etc.), substituted or unsubstituted 4
-Phenyl 1,3-butadienyl group (4-phenyl 1,3-butadienyl, 4-(p-methylphenyl) 1,3-butadienyl, etc.) or substituted or unsubstituted heterocyclic group (quinolyl, pyridyl, carbazolyl, furyl, etc.) ). Z is an anionic residue. Specific examples of Z in the general formulas (1) to (11) include perchlorate, fluoroborate,
Sulfoacetate, iodide, chloride, bromide, p-toluenesulfonate, alkylsulfonate, alkyldisulfonate,
Represents anionic residues such as benzenedisulfonate, halosulfonate, picrate, tetracyanoethylene anion, and tetracyanoquinodimethane anion. Specific examples of the azulenium salt compounds used in the present invention are listed below. Examples of compounds represented by the above general formula (1) Examples of compounds represented by the above general formula (2) Examples of compounds represented by the above general formula (3) Examples of compounds represented by the above general formula (4) Examples of compounds represented by the above general formula (5) Examples of compounds represented by the above general formula (6) Examples of compounds represented by the above general formula (7) Examples of compounds represented by the above general formula (8) Examples of compounds represented by the above general formula (9) Examples of compounds represented by the above general formula (10) Examples of compounds represented by the above general formula (11) Compounds represented by general formulas (1) and (2) are described in Angewandte Chemie, Vol. 78,
No. 20, P. 937 (1966), it can be easily obtained by reacting an azulene compound with squaric acid or croconic acid in an appropriate solvent. In the compound represented by the general formula (3), the compound where n=0 is
Chemical Society, (Journal of the
Chemical Society) P. 501 (1960) by heating the 1-formyl-azulene compound and the azulene compound in a suitable solvent in the presence of a strong acid; the
by mixing a 1-ethoxymethylene azulenium salt compound and an azulene compound in a suitable solvent as described in Journal of the Chemical Society) P.1724 to P.1730 (1961), or by mixing a 1-ethoxymethylene azulenium salt compound and an azulene compound in a suitable solvent, (Journal of the
Chemical Society) P. 359 (1961), by heating 2-hydroxymethylenecyclohexanone and an azulene compound in a suitable solvent in the presence of a strong acid. In general formula (3),
Compounds with n=1 and n=2 are described in the Journal of the Chemical Society.
the chemical society) P.3591-P.3592 (1961)
It can be obtained by mixing an azulene compound and malondialdehydes or glutacondialdehydes in a suitable solvent in the presence of a strong acid as described in . The compound represented by general formula (4) is a journal
of the Chemical Society, (Journal
of the chemical Society) P. 3588 (1961), it can be easily obtained by heating an azulene compound and glyoxal in a suitable solvent in the presence of a strong acid. The compound represented by general formula (5) is a journal
of the Chemical Society, (Journal
of the chemical Society) P. 501 (1960), by heating a 1,3-diformyl azulene compound and an azulene compound in a suitable solvent in the presence of a strong acid. The compound represented by general formula (6) is a journal
of the chemical, (Journal of the
1-formyl azulene compound and a heterocyclic quaternary ammonium salt compound having an active methyl group are heated in an appropriate solvent as described in P.163-P.167 (1961) It can be obtained by Compounds represented by general formulas (7), (8), (9) and (10) are listed in the Journal of the Chemical Society.
P.1110-P.1117 (1958), Journal of the Chemical Society,
Chemical Society) P.494-P.501 (1960) and Journal of the Chemical Society, P.3579
3593 (1961) by mixing an azulene compound and a corresponding aldehyde compound in a suitable solvent in the presence of a strong acid. The compound represented by the general formula (11) can be obtained by reacting a 1-formyl-azulene compound with a compound represented by the general formula (12) in a solvent. General formula (12) In the formula, X ₂ , Y, R ₁₃ , R ₁₄ , Z 2 and l have the same definitions as above. Reaction solvents used include alcohols such as ethanol, butanol and benzyl alcohol, nitriles such as acetonitrile and propionitrile, organic carboxylic acids such as acetic acid, acid anhydrides such as acetic anhydride, and alicyclics such as dioxane and tetrahydrofuran. Formula ethers, etc. are used.
Furthermore, aromatic hydrocarbons such as benzene can be mixed with butanol, benzyl alcohol, and the like. The temperature during the reaction can be selected from the range of room temperature to boiling point. The coating containing the azulenium salt compound described above exhibits photoconductivity and can therefore be used in the photosensitive layer of the electrophotographic photoreceptor described below. The coating containing the azulenium salt compound described above exhibits photoconductivity and can therefore be used in the photosensitive layer of the electrophotographic photoreceptor described below. That is, in a specific example of the present invention, the above-mentioned azulenium salt compound is formed on a conductive support by vacuum evaporation, or dissolved or dispersed in an appropriate binder to form a film, thereby allowing electrophotographic sensitization. body 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 which is functionally separated into a photosensitive layer, 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 a thin film layer having a thickness of 0.01 micron to 1 micron. 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 dissolving or dispersing the above-mentioned compound in a suitable binder and coating it on the substrate, or it can be obtained by forming a vapor deposited film using a vacuum vapor deposition device. I can do it. The binder used to form the charge generating layer by coating can be selected from a wide range of insulating resins and organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polyvinylpyrene. can. Preferably, polyvinyl butyral, polyarylate (condensation polymer of bisphenol A and phthalic acid, etc.), polycarbonate, polyester, phenoxy resin, polyvinyl acetate, acrylic resin,
Polyacrylamide resin, polyamide, polyvinylpyridine, cellulose resin, urethane resin,
Examples include insulating resins such as epoxy resin, casein, polyvinyl alcohol, and polyvinylpyrrolidone. The resin contained in the charge generation layer is suitably 80% by weight or less, preferably 40% by weight or less. Solvents that dissolve these resins vary depending on the type of resin, and specific organic solvents that are preferably selected from those that do not dissolve the charge transport layer or undercoat layer include methanol, ethanol, Alcohols such as isopropanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, N,N-dimethylformamide,
Amides such as N,N-dimethylacetamide,
Sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monomethyl ether, esters such as methyl acetate and ethyl acetate, aliphatic halogens such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, and trichloroethylene. Hydrocarbons or aromatics such as benzene, toluene, xylene, ligroin, monochlorobenzene, dichlorobenzene, etc. can be used. Coating can be carried out using coating methods such as dip coating, spray coating, spinner coating, bead coating, Meyer bar coating, blade coating, roller coating, and curtain coating. For drying, it is preferable to dry to the touch at room temperature and then heat dry. Heat drying at a temperature of 30℃ to 200℃ for 5 minutes to 2
It can be carried out stationary or under blown air for a period of time within a range of hours. 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. ing. At this time, this charge transport layer 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. 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" that includes gamma 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 trap each other, resulting in a decrease in sensitivity. Charge transport substances include electron transport substances and hole transport substances, and electron transport substances include chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, and 2,4,7-trinitro-9-fluorenone. , 2, 4, 5, 7-
Tetranitro-9-fluorenone, 2,4,7-
trinitro-9-dicyanomethylenefluorenone, 2,4,5,7-tetranitroxanthone,
Examples include electron-withdrawing substances such as 2,4,8-trinitrothiosanthone, and polymerization of these electron-withdrawing substances. Examples of hole-transporting substances include pyrene, N-ethylcarbazole, N-isopropylcarbazole,
N-Methyl-N-phenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-3-methylidene-9-ethylcarbazole, N,N-diphenylhydrazino-
3-methylidene-10-ethylphenothiazine,
N,N-diphenylhydrazino-3-methylidene-10-ethylphenoxazine, 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-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-hydrazone hydrazones such as 2,5-bis(P-diethylaminophenyl)-1,3,4-oxadiazole, 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) pyrazoline, 1-[6
-methoxy-pyridyl(2)]-3-(P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(3)]-3-(P-
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[lepidyl(2)]-
3-(P-diethylaminostyryl)-5-(P-
diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(P-diethylaminostyryl)
-4-Methyl-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)]-3-(α-
Methyl-P-diethylaminostyryl)-5-(P
-diethylaminophenyl)pyrazoline, 1-phenyl-3-(P-diethylaminostyryl)-4
-Methyl-5-(P-diethylaminophenyl)
Pyrazoline, 1-phenyl-3-(αbenzyl-
P-diethylaminostyryl)-5-(P-diethylaminophenyl)-pyrazoline, spiropyrazoline and other pyrazolines, 2-(P-diethylaminostyryl)-6-diethylaminobenzoxazole, 2-(P-diethylaminophenyl)-4
-(P-diethylaminophenyl)-5-(2-chlorophenyl)oxazole and other oxazole compounds, 2-(P-diethylaminostyryl)-6
-thiazole compounds such as diethylaminobenzothiazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, 1,1-bis(4-N,N-diethylamino-2-methylphenyl)heptane, 1 ,1,2,2-tetrakis(4-N,N-
Polyarylalkanes such as dimethylamino-2-methylphenyl)ethane, triphenylamine, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polyvinylacridine, poly-9-vinylphenylanthracene, pyrene-formaldehyde resin, ethyl Examples include carbazole 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. Moreover, these charge transport substances may be one or two types.
More than one species can be used in combination. When the charge transport material does not have film-forming properties,
A film can be formed by selecting an appropriate binder. Resins that can be used as binders are:
For example, insulating resins such as acrylic resin, polyarylate, polyester, polycarbonate, polystyrene, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral, polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorinated rubber furnace, or poly-N- Examples include organic photoconductive polymers such as 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 between 5 microns and 30 microns, with a preferred range between 8 microns and 20 microns. When forming the charge transport layer by coating, an appropriate coating method as described above can be used. A photosensitive layer having such a laminated structure of a charge generation layer and a charge transport layer is provided on a substrate having a conductive layer. As the substrate having the conductive layer, materials that are conductive themselves such as aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, isodium, gold, and platinum can be used. Plastics (e.g., polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, acrylic resin, polyethylene fluoride, etc.), conductive particles (e.g. carbon black,
A substrate made of plastic coated with silver particles, etc.) together with a suitable binder, 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 subbing layer is made of 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. The thickness of the undercoat layer is 0.1 micron to 5 micron.
Preferably, 0.5 micron to 3 micron is appropriate. When using a photoreceptor in which a conductive layer, a charge generation layer, and a charge transport layer are stacked 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 charge, causing a decrease in surface potential and creating an electrostatic contrast with the unexposed area. . A visible image can be obtained by developing the electrostatic latent image thus obtained with a negatively charged toner. This can be directly fixed, or the toner image can be transferred to paper, plastic film, etc. and then developed and fixed. Alternatively, a method may be used in which the electrostatic latent image on the photoreceptor 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 is composed of a pore transport material, the surface of the charge transport layer must be negatively charged.
After charging, when exposed to light, the raw pores 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 negative charge, causing a decrease in surface potential and static electricity between the exposed area and the unexposed area. Electrocontrast occurs. During development, it is necessary to use a positively charged toner, contrary to the case where an electron transporting substance is used. In another specific example of the present invention, organic photoconductive materials such as the aforementioned hydrazones, pyrazolines, oxazoles, thiazoles, triarylmethanes, polyarylalkanes, triphenylamines, poly-N-vinylcarbazoles, etc. The photosensitive coating may contain the above-mentioned compounds as sensitizers for inorganic photoconductive substances such as photoconductive substances, zinc oxide, cadmium sulfide, and selenium. This photosensitive film is formed by coating these photoconductive substances and the above-mentioned compounds together with a binder. In any photoreceptor, the general formula [],
This photosensitive material contains at least one kind of azulenium salt selected from the compounds represented by [ ] or [ ], and is optionally used in combination with other photoconductive pigments or dyes with different light absorption. It is also possible to increase the sensitivity of the body or to prepare it as a panchromatic photoreceptor. Hereinafter, the present invention will be explained according to examples. Examples 1 to 17 Ammonia aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water, 222 ml of water) on an aluminum plate
was applied with a Mayer bar so that the film thickness after drying was 1.0 microns, and dried. Next, 17 types of coating liquids were prepared by adding 5 g of each of the 17 types of azulenium salts listed in the table below to a solution of 2 g of butyral resin (butyralization degree: 63 mol %) dissolved in 95 ml of isopropyl alcohol. After each coating liquid is dispersed with an attritor, the dry film thickness is
Apply with a Mayer bar to a thickness of 0.1 micron,
A charge generation layer was formed by drying. Then, the structural formula Dissolve 5 g of hydrazone compound and 5 g of polymethyl methacrylate resin (number average molecular weight 100.000) in 70 ml of benzene, apply this onto the charge generation layer using a Mayer bar so that the dry film thickness is 12 microns, and dry. A charge transport layer was formed. The 17 types of electrophotographic photoreceptors prepared in this way were tested using an electrostatic copying paper tester, ModeSP-, manufactured by Kawaguchi Electric Co., Ltd.
428 using a static method with a corona charge of -5KV, held in a dark place for 10 seconds, and then exposed to light at an illuminance of 5lux to examine charging characteristics. The charging characteristics are the initial charging potential (V _O ) and 10
The amount of exposure (E1/2) required to attenuate the potential to 1/2 when dark decaying for a second was measured. The results are shown in Table 1. Further, the charge retention rate when dark decayed for 10 seconds was expressed as V _K (%).

[Table] Example 18 Polyester resin (manufactured by Toyobo Co., Ltd., Byron
200) 5g and 1-[pyridyl-(2)]-3-(4-N,
N-diethylaminostyryl)-5-(4-N,N
-Diethylaminophenyl) pyrazoline was dissolved in 80 ml of methyl ethyl ketone, and then 1.0 g of the azulenium salt compound No. (25) mentioned above was added and dispersed.
A photoreceptor having a photosensitive layer with a dry film thickness of 13 microns was prepared by coating and drying on a polyester film deposited with aluminum. The characteristics of this photoreceptor were determined using the same method as in Example 1 to determine the initial charging potential (V _O ), the charge retention rate (V _K ) when dark decayed for 10 seconds, and the charging potential when dark decay was carried out for 10 seconds. The exposure amount (E1/2) required to attenuate the amount of light to 1/2 was measured and found to be as follows. V _O : -560V V _K : 84% E1/2: 42.0lux・sec Examples 19-29 Instead of the azulenium salt compound (25) used when preparing the photoreceptor of Example 26, the compounds listed in the table below were used. A photoreceptor was prepared in exactly the same manner as in Example 18, except that the azulenium salt compound was used.
The charging characteristics of each photoreceptor were measured. These results are shown in Table 2.

[Table] Example 30 1 g of poly-N-vinylcarbazole and 5 mg of the aforementioned azulenium salt compound No. (24) were added to 10 g of 1,2-dichloroethane, and the mixture was thoroughly stirred. The coating solution 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 determined.
The results are shown below. V _O : +420V V _K : 78% E1/2: 45.8lux・sec Example 31 The azulenium salt compound described above was used in place of the azulenium salt compound (24) used when preparing the electrophotographic photoreceptor of Example 30. Except for using No. (1),
A photoreceptor was prepared in exactly the same manner as in Example 30, and then the charging characteristics of this photoreceptor were measured. The results are shown below. However, the charging polarity was determined. V _O : +490V V _K : 82% E1/2: 29.8lux・sec Example 32 Particulate zinc oxide (Sazex2000 manufactured by Sakai Chemical Co., Ltd.) 10
g, 4 g of acrylic resin (Dyanal LR009 manufactured by Mitsubishi Rayon Co., Ltd.), 10 g of toluene, and 10 mg of the above-mentioned azulenium salt compound No. (24) were thoroughly mixed in a ball mill, and the resulting coating liquid was applied to aluminum. It was applied onto the vapor-deposited polyethylene terephthalate film using a doctor blade to a dry film thickness of 21 microns, 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 was more sensitive to long wavelengths than the zinc oxide coating that did not contain the azulenium salt compound mentioned above. It was found that it has. Example 33 An ammonium aqueous solution of casein was applied onto a 100 micron thick aluminum plate and dried to a film thickness of 1.1
A micron subbing layer was formed. Next, 5 g of 2,4,7-trinitro-9-fluorenone and 5 g of poly-N-vinylcarbazole (number average molecular weight 300,000) were added to 70 ml of tetrahydrofuran.
to form a charge transfer complex. This charge transfer complex compound and the aforementioned azulenium salt compound No.
(31) 1 g was added to a solution in which 5 g of polyester resin (Vylon, manufactured by Toyobo) was dissolved in 70 ml of tetrahydrofuran, and dispersed. This dispersion was applied onto the undercoat layer so that the film thickness after drying was 12 microns, and dried. The charging characteristics of the photoreceptor thus prepared were measured in the same manner as in Example 1. These results were as follows. However, the charging polarity was determined. V _O : +430V V _K : 83% E1/2 : 7.5lux·sec Example 34 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, the coating solution containing the azulenium salt compound of Example 13 was applied onto the previously formed polyvinyl alcohol layer using a Mayer bar so that the film thickness after drying was 0.1 micron, dried and charged. A generation layer was formed. In the following, the structural formula A solution prepared by dissolving 5 g of pyrazoline compound and 5 g of polyarylate resin (condensation polymer of bisphenol A and terephthalic acid-isophthalic acid) in 70 ml of tetrahydrofuran is placed on the charge generation layer so that the film thickness after drying is 10
It was applied to a micron thickness and dried to form a charge transport layer. Example 1 shows the charging characteristics of the photoreceptor thus prepared.
It was measured using the same method as above. The results are shown below. V _O : -545V V _K : 87% E1/2: 3.4lux・sec Example 35 An ammonia aqueous solution of casein (11.2 g of casein, 1 g of 28% ammonia water, 222 ml of water) was coated on an aluminum cylinder using the dip coating method. death,
It was dried to form a subbing layer with a coating weight of 1.0 g/m ² . Next, 1 part by weight of the aforementioned azulenium salt compound No. (30) and butyral resin (Eslec BM-
2: 1 part by weight (manufactured by Sekisui Chemical Co., Ltd.) and 30 parts by weight of isopropyl alcohol were dispersed for 4 hours using a ball mill disperser. This dispersion was applied onto the previously formed subbing layer by a dip coating method and dried to form a charge generation layer. The film thickness at this time was 0.3 microns. Next, P-diethylaminobenzaldehyde-
1 part by weight of N-phenyl-N-α-naphthylhydrazone, 1 part by weight of polysulfone resin (P1700: manufactured by Union Carbide), and 6 parts by weight of monochlorobenzene.
Parts by weight were mixed and dissolved by stirring with a stirrer. This liquid was applied onto the charge generation layer by dip coating and dried to form a charge transport layer. The film thickness at this time was 12 microns. A -5KV corona discharge was applied to the photoreceptor thus prepared. The surface potential at this time was measured (initial potential _VO ). Furthermore, the surface potential of this photoreceptor was measured after discharging it in the dark for 5 seconds (dark decay V _K ).
Sensitivity is the amount of exposure required to attenuate the potential V _K to 1/2 after dark decay (E1/2 microjoules/cm ² )
It was evaluated by measuring. At this time, a gallium aluminum arsenide semiconductor laser (oscillation wavelength 780 nm) was used as a light source. These results were as follows. V _O : -540V V _K : 87% E1/2: 2.0 microjoules/ ^cm2 Examples 36 to 45 Azulenium salt compound No. used in Example 35.
A photoreceptor was prepared in exactly the same manner as in Example 35, except that the compounds shown in Table 3 were used in place of (30), and the characteristics of this photoreceptor were measured. These results are shown in Table 3.

【table】

Claims (1)

[Scope of Claims] 1. A photoconductive film comprising an azulenium salt compound represented by the following general formula [], [] or []. general formula [In general formulas [], [] and [],
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a halogen atom or a monovalent organic residue, and X represents a substituted or unsubstituted 5-, 6-, or 7-membered aromatic ring. Represents the atomic group necessary for formation. Furthermore, an aromatic ring formed by R ₁ and X, an aromatic ring formed by X and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₄ and
In at least one combination of R ₅ combinations,
A ring may be formed by a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain, Z represents an anion residue, and A represents a divalent group represented by the following general formulas (1) to (11). Represents an organic residue. However, general formula (1) to
Q in (11) is the following formula (In the formula, R ₁ to R ₅ and X are the same as above.) The right side excluding Q represents A. General formula (1) (In the formula, R ₁ to R ₅ and X are the same as above.) General formula (2) (In the formula, R ₁ to R ₅ and X are the same as above.) General formula (3) (In the formula, R' ₁ to R' ₅ are hydrogen atoms, halogen atoms, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted aralkyl groups, acyl groups, substituted or unsubstituted X' forms a substituted or unsubstituted 5-, 6-, or 7-membered aromatic ring.Also, the aromatic ring of R' ₁ and X', the aromatic ring of X'
Aromatic rings, heterocycles, or aliphatic rings substituted or unsubstituted with at least one combination of R' ₂ , R' ₂ and R' ₃ , R' ₃ and R' ₄ , and R' ₄ and R' ₅ . A ring may be formed by a group chain. Further, the azulenium skeleton represented by Q may be symmetrical or asymmetrical. Z represents an anionic residue. _R6 is
It represents a hydrogen atom, a nitro group, a cyano group, an alkyl group or an aryl group, and n represents 0, 1 or 2. ) General formula (4) (In the formula, R ₁ to R ₅ , X and Z are the same as above.) General formula (5) (In the formula, R ₁ to R ₅ , X and Z have the same definitions as defined above. R″ ₁ to R″ ₆ are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl group, acyl group, substituted or unsubstituted amino group, substituted or unsubstituted styryl group, nitro group, hydroxy group, mercapto group, thioether group, carboxyl group, carboxylic acid ester, carboxylic acid amide, cyano group, or substituted or unsubstituted arylazo group. Also, R″ ₂ , R″ ₃ , R″ ₃
and R″ ₄ , R″ ₄ and R″ ₅ , and R″ ₅ and R″ ₆ , at least one combination forms a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain ring. ) General formula (6) ( _wherein , represents a group of nonmetallic atoms necessary for , and such a heterocycle may be substituted with a halogen atom, an alkyl group, or an aryl group. R ₇ is a substituted or unsubstituted alkyl group,
It represents a cyclic alkyl group, an allyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, m represents 0 or 1, and Z is the same as above. ) General formula (7) Q = CH-R ₈ Z (In the formula, R ₈ represents a substituted or unsubstituted aryl group, and Z is the same as above.) General formula (8) Q = CH- R ₉ Z (wherein R ₉ represents a monovalent heterocyclic group derived from furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine, pyridine,
is the same as above. ) General formula (9) (In the formula, R ₁₀ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and R ₈ and Z are the same as above.) General formula (10) Q = CH-C≡C- R ₈ Z (In the formula, R ₈ and Z are the same as above.) General formula (11) ( _wherein ,
Shows the atomic groups necessary to complete naphthothiapyran or naphthoselenapyran. 1 is 0 or 1. Y represents a sulfur atom, an oxygen atom or a selenium atom. R ₁₁ and R ₁₂ are hydrogen atoms, alkyl groups,
represents 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 heterocyclic group, and Z represents the above-mentioned It is the same as the thing. )] 2 On the conductive support, the following general formula [],
An electrophotographic photoreceptor comprising a photosensitive layer containing an azulenium salt compound represented by [ ] or [ ]. general formula [In general formulas [], [] and [],
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent a hydrogen atom, a halogen atom or a monovalent organic residue, and X represents a substituted or unsubstituted 5-, 6-, or 7-membered aromatic ring. Represents the atomic group necessary for formation. Furthermore, an aromatic ring formed by R ₁ and X, an aromatic ring formed by X and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , and R ₄ and
In at least one combination of R ₅ combinations,
A ring may be formed by a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain, Z represents an anion residue, and A represents a divalent group represented by the following general formulas (1) to (11). Represents an organic residue. However, general formula (1) to
Q in (11) is the following formula (In the formula, R ₁ to R ₅ and X are the same as above.) The right side excluding Q represents A. General formula (1) (In the formula, R ₁ to R ₅ and X are the same as above.) General formula (2) (In the formula, R ₁ to R ₅ and X are the same as above.) General formula (3) (In the formula, R' ₁ to R' ₅ are hydrogen atoms, halogen atoms, substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, substituted or unsubstituted aralkyl groups, acyl groups, substituted or unsubstituted X' forms a substituted or unsubstituted 5-, 6-, or 7-membered aromatic ring.Also, the aromatic ring of R' ₁ and X', the aromatic ring of X'
Aromatic rings, heterocycles, or aliphatic rings substituted or unsubstituted with at least one combination of R' ₂ , R' ₂ and R' ₃ , R' ₃ and R' ₄ , and R' ₄ and R' ₅ . A ring may be formed by a group chain. Further, the azulenium skeleton represented by Q may be symmetrical or asymmetrical. Z represents an anionic residue. _R6 is
It represents a hydrogen atom, a nitro group, a cyano group, an alkyl group or an aryl group, and n represents 0, 1 or 2. ) General formula (4) (In the formula, R ₁ to R ₅ , X and Z are the same as above.) General formula (5) (In the formula, R ₁ to R ₅ , X and Z have the same definitions as defined above. R″ ₁ to R″ ₆ are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted aralkyl group, acyl group, substituted or unsubstituted amino group, substituted or unsubstituted styryl group, nitro group, hydroxy group, mercapto group, thioether group, carboxyl group, carboxylic acid ester, carboxylic acid amide, cyano group, or substituted or unsubstituted arylazo group. Also, R″ ₂ , R″ ₃ , R″ ₃
and R″ ₄ , R″ ₄ and R″ ₅ , and R″ ₅ and R″ ₆ , at least one combination forms a substituted or unsubstituted aromatic ring, heterocycle, or aliphatic chain ring. ) General formula (6) ( _wherein , represents a group of nonmetallic atoms, and such a heterocycle may be substituted with a halogen atom, an alkyl group, or an aryl group.
R ₇ represents a substituted or unsubstituted aryl group,
m represents 0 or 1, and Z is the same as above. General formula (7) Q = CH-R ₈ Z (In the formula, R ₈ represents a substituted or unsubstituted aryl group, and Z is the same as above.) General formula (8) Q = CH-R ₉ Z (wherein R ₉ represents a monovalent heterocyclic group derived from furan, thiophene, benzofuran, thionaphthene, dibenzofuran, carbazole, phenothiazine, phenoxazine, pyridine,
is the same as above. ) General formula (9) (In the formula, R ₁₀ represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, and R ₈ and Z are the same as above.) General formula (10) Q = CH-C≡C- R ₈ Z (In the formula, R ₈ and Z are the same as above.) General formula (11) ( _wherein ,
Shows the atomic groups necessary to complete naphthothiapyran or naphthoselenapyran. 1 is 0 or 1. Y represents a sulfur atom, an oxygen atom or a selenium atom. R ₁₁ and R ₁₂ are hydrogen atoms, alkyl groups,
represents 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 heterocyclic group, and Z represents the above-mentioned It is the same as the thing. )]