JPH0541987B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photoreceptor used in an electrophotographic process. To be more specific,
The present invention relates to an electrophotographic photoreceptor containing a novel squarerium compound in a photoconductive layer. Conventional technology Conventionally, amorphous selenium,
Inorganic photosensitive materials such as selenium alloys, cadmium sulfide, and zinc oxide, and organic photosensitive materials typified by polyvinylcarbazole and polyvinylcarbazole derivatives are widely known. It is well known that amorphous selenium or selenium alloys have extremely excellent properties as electrophotographic photoreceptors and are used in practical applications. However, its production requires a complicated step of vapor deposition, and the produced vapor-deposited film has the drawback of not being flexible. When zinc oxide is used, it is used as a dispersed photosensitive material in which zinc oxide is dispersed in a resin, but such a photosensitive material has a drawback in mechanical strength and cannot withstand repeated use as it is. Polyvinylcarbazole, which is widely known as an organic photoconductive material, has excellent advantages in terms of transparency, film-forming properties, and flexibility, but polyvinylcarbazole itself does not have sensitivity in the visible light range. , cannot be put to practical use as it is, and therefore various sensitization methods have been proposed. However, when polyvinylcarbazole is spectrally sensitized using a dye sensitizer, although the spectral sensitivity range is diffused into the visible light range, it still cannot provide sufficient sensitivity as an electrophotographic photoreceptor, and it suffers from photofatigue. It has a serious drawback. In addition, when chemically sensitized using an electron-accepting compound, a photoreceptor with sufficient sensitivity as an electrophotographic photoreceptor can be obtained, and some of them have been put into practical use. However, there are still problems with the product lifespan. In recent years, various types of organic electrophotographic photoreceptors have been studied, and it has been reported that, in particular, a laminated type photoreceptor having a charge generation layer and a charge transport layer has electrical properties superior to those of conventional photoreceptors. Known charge generating materials used in these electrophotographic photoreceptors include bisazos, trisazos, phthalocyanines, pyryliums, squareryliums, and the like. Phthalocyanines, trisazos, and squarerilliums have been reported to have sensitivity from the visible region to the near-infrared region.
Among these, regarding squarerium compounds, for example, JP-A-49-105536 and JP-A-Sho
It is described in Publication No. 58-21416. Problems to be Solved by the Invention However, phthalocyanines have disadvantages in that their spectral sensitivity is biased toward long wavelengths and poor red color reproducibility, while trisazo compounds have excellent electrical properties and sufficient sensitivity. do not have. Furthermore, the squareylium compound shown in JP-A-58-214162 has not yet achieved sufficient sensitivity, and the squarylium compound shown in JP-A-49-105536 has relatively high sensitivity. It has drawbacks in chargeability, dark decay, etc., and it has not been possible to achieve both high sensitivity and low dark decay. Therefore, an object of the present invention is to eliminate the above-mentioned drawbacks and provide an electrophotographic photoreceptor that has spectral sensitivity from the visible region to the near-infrared region, and has high sensitivity and excellent electrical properties. be. Means for Solving the Problems The above objects of the present invention can be achieved by using an asymmetric squarerium compound represented by the following general formula () as a photosensitive material for an electrophotographic photoreceptor. Therefore, the electrophotographic photoreceptor of the present invention is characterized by having a photosensitive layer containing an asymmetric squarerylium compound represented by the following general formula (). (In the formula, R ₁ and R ₂ each have 1 to 20 carbon atoms.
represents an alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R ₃ is a hydrogen atom, a hydroxyl group, a methyl group, a trifluoromethyl group, a halogen atom, a carboxyl group, an alkylcarbonylamino group. or represents an alkylsulfonylamino group, R ₄ is a hydrogen atom,
represents a hydroxyl group or an alkyl group, R ₅ represents a hydrogen atom, an alkyl group, an alkoxycarbonyl group, or a substituted or unsubstituted carbamoyl group; R ₆
represents an alkyl group, and n represents an integer from 0 to 5. ) Specific examples of the squarerium compound used in the electrophotographic photoreceptor of the present invention include the following. These squarylium compounds include, for example, squarylium chloride and general expression () (In the formula, R ₁ to _{R 3} have the same meanings as described above.) After reacting the aniline derivative represented by the following in a Friedel-Crafts type reaction and hydrolyzing the obtained cyclobutenedione derivative, the general formula () (In the formula, R ₄ to _{R 6} have the same meanings as described above.) It can be synthesized by heating and reacting with an azulene derivative represented by the following in an organic solvent. An example is shown below. Synthesis example: 7.5 g (0.050 mol) of squaric acid chloride and 6.5 ml (0.050 mol) of boron trifluoride ethyl ether complex.
Dissolve 35 g (0.25 mol) of N,N-dimethyl-m-fluoroaniline in 30 ml of methylene chloride.
The mixture was stirred at room temperature for 16 hours to carry out the reaction. After the reaction was completed, the mixture was washed with dilute hydrochloric acid and then with water.
Separation and purification was performed using column chromatography, and 3-chloro-4-(4'-dimethylamino-
2'-fluorophenyl)-3-cyclobutene-1,
9.1 g (yield 72%) of 2-dione was obtained. Next, 60 ml of acetic acid and 20 ml of water were added to 9.1 g (0.039 mol) of the obtained compound, and the mixture was heated under reflux for 1 hour.
After cooling, the precipitate was filtered, washed with water, and 3-
(4'-dimethylamino-2'-fluorophenyl)-
8.5 g (yield 92%) of 4-hydroxy-3-cycloptene-1,2-dione was obtained. Obtained 4-hydroxycyclobutene derivative
0.67 g (2.8 mmol) and 0.75 g (2.8 mmol) of 1-phenylcarbamoyl-2-hydroxyazulene were suspended in 100 ml of butanol and heated under reflux for 5 hours. The mixture was allowed to cool, the precipitate was separated by filtration, washed with methanol and ether, and exemplified compound No. 11 was obtained.
1.16 g (yield 86%) was obtained. Melting point: 291℃ (decomposed) Infrared absorption spectrum: Figure 3 Elemental analysis: as C ₂₉ H ₂₁ FN ₂ O ₄

[Table] Other squareryllium compounds exemplified above also include
It can be synthesized in the same manner as above. In the present invention, the squarylium compound represented by the general formula () is contained in the photosensitive layer of an electrophotographic photoreceptor, and it is preferably used in an electrophotographic photoreceptor in which the photosensitive layer has a multilayer structure. That is, in an electrophotographic photoreceptor including a photosensitive layer with a two-layer structure consisting of a charge generation layer and a charge transport layer, high sensitivity and chargeability can be achieved by providing a charge generation layer containing a squareryllium pigment and a known charge transport layer. , an electrophotographic photoreceptor with improved electrical properties such as dark decay can be obtained. A case where the electrophotographic photoreceptor of the present invention has a photosensitive layer having the above-mentioned two-layer structure will be explained with reference to the drawings. As shown in FIGS. 1 and 2, a squarerium compound is A photosensitive layer 4 is provided, which is a laminate of a charge generation layer 2 containing a charge transport material and a charge transport layer 3 containing a charge transport substance. The stacking order of the charge generation layer 2 and the charge transport layer 3 is arbitrary. In this case, a protective layer may be provided on the photosensitive layer 4, or an intermediate layer may be provided between the photosensitive layer 4 and the conductive support 1. The charge generation layer may be formed of a squarerylium compound alone, but it can also be formed in combination with a binder resin. In the latter case, the proportion of squarerium compound to binder resin is from 10% to 90% by weight, preferably from 20% to 70% by weight. When using a binder resin, the binder resin itself may or may not have photoconductivity. Examples of the binder resin having photoconductivity include photoconductive polymers such as polyvinylcarbazole, polyvinylcarbazo derivatives, polyvinylnaphthalene, polyvinylanthracene, and polyvinylpyrene, and other organic matrix materials having charge transport ability. Furthermore, as the binder resin that does not have photoconductivity, a known insulating resin can be used.
Examples of these known insulating resins include polystyrene, polyester, polyvinyltoluene, polyvinylanisole, polychlorostyrene, polyvinyl butyral, polyvinyl acetate, polyvinyl butyl methacrylate, copolystyrene-butadiene, polysulfone, copolystyrene-methyl methacrylate, and polycarbonate. It will be done. At this time, in order to further improve the mechanical strength of the resulting electrophotographic photoreceptor, a plasticizer can be used in the same manner as in general polymeric materials. As a plasticizer,
For example, chlorinated paraffin, chlorinated biphenyl,
Phosphate plasticizers, phthalate plasticizers, etc. can be used, and the binder resin has a zero
By adding up to 10% by weight, it is possible to further improve the mechanical strength of the electrophotographic photoreceptor without deteriorating its sensitivity or electrical properties. The thickness of the charge generation layer is 0.05 to 3μ, preferably 0.1
~1μ. The charge generation layer is formed by a well-known method. That is, when forming a charge generation layer using a squarerium compound alone without using a binder resin,
Solvent coating and vacuum deposition methods can be used. Further, when a binder resin is used in combination, the squarerium compound is crushed and then dispersed in the binder resin. As the grinding method, known methods such as SPEL MILL,
Ball mills, RED DEVIL (product name), etc. can be used. The binder resin in which the squarerium compound is dispersed is coated on the charge transport layer or the conductive support. Coating methods include a dipping method, a spray method, a bar coater method, and an applicator method, and a good charge generation layer can be formed by any of these methods. On the other hand, as a charge transport layer, N-methyl-N-
Phenylhydrazinone-3-methylidene-9-ethylcarbazole, p-diethylaminobenzaldehyde-N,N-diphenylhydrazone, p-
Hydrazones such as diethylaminobenzaldehyde-N-α-naphthyl-N-phenylhydrazone, 1-phenyl-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline, 1-[quinoline (2) ]-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline and other pyrazolines, 2-(p-diethylaminophenyl)
oxazole compounds such as -diethylaminostyryl)-6-diethylaminobenzoxazole, triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane, N,N'-diphenyl-N,N'-bis- (3-methylphenyl)-(1,1'-biphenyl)
-Binder resin containing diamine compounds such as -4,4'-diamine, or poly-N
- Photoconductive polymers such as vinylcarbazole, polyvinylanthracene, etc. are used. Further, as the conductive support, metal, paper treated with conductivity, a polymer film having a conductive layer, glass, etc. can be used. Examples Next, the present invention will be explained by examples. Example 1 To 1 part by weight of Exemplified Compound No. 2, 1 part by weight of polyester resin (Adhesive 49000, manufactured by Dupont) and 10 parts by weight of tetrahydrofuran were added, and the resulting dispersion was ground and mixed in a ball mill for 4 hours, and then coated with aluminum using a bar coater. was coated on a polyester film [Metal Me (registered trademark) manufactured by Toray Industries, Ltd.] on which the mixture had been vapor-deposited, and dried at 70° C. for 5 hours to form a charge generation layer with a thickness of 1 μm. On this charge generation layer, N,N'-diphenyl-
N,N'-bis-(3-methylphenyl)-[1,
A homogeneous solution consisting of 1 part by weight of 1'-biphenyl]-4,4' diamine, 1 part by weight of polycarbonate resin (manufactured by Teijin, Panlite (registered trademark)) and 10 parts by weight of tetrahydrofuran was applied using an applicator. It was dried at ℃ for 16 hours to form a charge transport layer with a thickness of 22 μm, and an electrophotographic photoreceptor was prepared.
SP-428), the photosensitive layer is negatively charged by -6kV corona discharge, left in a dark place for 2 seconds, and then a tungsten lamp is used to illuminate the photosensitive layer so that the surface illuminance is 10 lux. Irradiation was performed, and an exposure amount E1/2 was determined so that the surface potential became 1/2 of the surface potential V _D after being left in a dark place. The results are the initial charging potential Vo = -900V, and the potential after being left in the dark for 2 seconds.
V _DDP =-880V, E1/2 = 4.2 lux·sec, and residual potential Rp = 0V. In addition, the following measurements were performed to demonstrate that the material has extremely excellent sensitivity to long wavelength light. After charging the above photoconductor by corona discharge in a dark place, use a monochromator to charge it.
The photoreceptor was irradiated with monochromatic light of 1 μW/cm ² at 800 nm. Then, the amount of exposure was determined by measuring the time it took for the surface potential to decrease to 1/2. The result is
It was 19.2erg/ ^cm2 . Examples 2 to 8 In Example 1, as shown in Table 1, Exemplified Compounds No. 5, 6, 7, 11, 12, 13 and
Electrophotographic photoreceptors were prepared in the same manner as in Example 1, except that No. 16 (Examples 2 to 8, respectively) were used, and the characteristics thereof were evaluated. The results obtained are shown in Table 1.

[Table] Effects of the Invention The electrophotographic photoreceptor of the present invention has a photosensitive layer containing a squareryllium compound that has spectral sensitivity from the visible region to the near-infrared region and has high sensitivity and excellent electrical properties. It has excellent electrical properties such as chargeability and dark decay, and can be widely used not only in copying machines but also in semiconductor laser printers and the like.

[Brief explanation of the drawing]

FIGS. 1 and 2 are schematic diagrams showing cross-sectional views of the electrophotographic photoreceptor of the present invention, and FIG. 3 is an infrared absorption spectrum of an example of the squarerylium compound used in the present invention. DESCRIPTION OF SYMBOLS 1... Conductive support, 2... Charge generation layer, 3... Charge transport layer, 4... Photosensitive layer.

Claims (1)

[Claims] 1 General formula () (In the formula, R ₁ and R ₂ each have 1 to 20 carbon atoms.
represents an alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and R ₃ is a hydrogen atom, a hydroxyl group, a methyl group, a trifluoromethyl group, a halogen atom, a carboxyl group, an alkylcarbonylamino group. or represents an alkylsulfonylamino group, R ₄ is a hydrogen atom,
represents a hydroxyl group or an alkyl group, R ₅ represents a hydrogen atom, an alkyl group, an alkoxycarbonyl group, or a substituted or unsubstituted carbamoyl group; R ₆
represents an alkyl group, and n represents an integer from 0 to 5. ) An electrophotographic photoreceptor comprising a photosensitive layer containing an asymmetric squarerium compound represented by: 2 The squarerium compound is represented by the above general formula (), where R ₁ and R ₂ each represent a lower alkyl group or a benzyl group, and R ₃ is a hydrogen atom,
Represents a hydroxyl group, methyl group or halogen atom,
The electron according to claim 1, wherein R ₄ represents a hydrogen atom or a hydroxyl group, R ₅ represents a hydrogen atom, a lower alkyl group, an alkoxycarbonyl group, or a phenylcarbamoyl group, and n represents 0. Photographic photoreceptor.