JPH05165238A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body having high sensitivity, being low in residual potential, being high in electrifying ability and having a reduced variation when repeated, especially being favorable in electrifying stability affecting to a picture density, being usable as a sensitive body having high durability, and at the same time, having high sensitivity at a wavelength range of 750-850nm, especially being suitable for photosensitive body of a semiconductor laser printer. CONSTITUTION:In a electrophotographic sensitive body providing a photosensitive layer containing a charge generating material and a charge conveying material on a electric conductive supporting body, dihalogeno-tin-phthalocianine is used as an electric charge generating material and 1-pyrene carbaldehydhydrazone, etc., is used as a electric charge conveying material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photoreceptor using dihalogenotin phthalocyanine as a charge generating material and 1-pyrenecarbaldehydehydrazones as a charge transporting material.

[0002]

2. Description of the Related Art Conventionally, photoconductive substances such as selenium, cadmium sulfide, and zinc oxide have been widely used in the photosensitive layer of electrophotographic photoreceptors. In addition, research has been conducted on the use of an organic photoconductive substance typified by polyvinylcarbazole in the photosensitive layer of an electrophotographic photoreceptor, and some of them have been put to practical use. Organic photoconductive materials have advantages over inorganic materials in that they are lighter in weight, easier to form a film, easier to manufacture a photoconductor, and non-polluting materials. ..

Further, in recent years, a laser beam printer (LBP), etc., which has advantages of high speed, high image quality and non-impact using a laser beam as a light source instead of the conventional white light, has been widely spread along with the progress of information processing systems. Therefore, there is a demand for the development of a material capable of withstanding the demand.

Particularly, among the laser beams, semiconductor lasers, whose applications have recently been increasing in compact discs, optical discs, etc. and whose technological progress has been remarkable, have been actively applied in the printer field as compact and highly reliable optical raw materials. In this case, since the wavelength of the light source is around 800 nm, there is a strong demand for development of a photoconductor having high sensitivity to long wavelength light around 800 nm. Examples of materials that meet this purpose include dihalogenotin phthalocyanines (see JP-A-62-119547). However, there has been a demand for an optical body having high sensitivity to long-wavelength light and practical electric characteristics (chargeability, residual potential, repeated stability, etc.).

The inventors of the present invention have made earnest studies on an electrophotographic photosensitive member using a dihalogenotin phthalocyanine. As a result, the dihalogenotin phthalocyanine is used as a charge generating material, and 1-pyrenecarbaldehyde hydrazone is used as a charge transporting material. The inventors have found that the combination of the above-mentioned ones has a very good sensitivity, chargeability, dark decay, residual potential and the like as an electrophotographic photoreceptor and has very excellent electrical characteristics, and thus completed the present invention.

That is, an object of the present invention is to use dihalogenotin phthalocyanine and 1-pyrenecarbaldehyde hydrazone compounds which are highly sensitive to near infrared light for semiconductor lasers, have excellent electrical characteristics, and are easy to manufacture. 750-850
It is an object of the present invention to provide an electrophotographic photoreceptor having high sensitivity to long-wavelength light near nm and having other good electrical characteristics.

[0007]

SUMMARY OF THE INVENTION However, the gist of the present invention is to use a dihalogeno compound as a charge generating material in an electrophotographic photoreceptor having a photosensitive layer containing a charge generating material and a charge transporting material on a conductive support. Using tin phthalocyanine,
The present invention relates to an electrophotographic photoreceptor characterized by using 1-pyrenecarbaldehydehydrazones as a charge transport material.

Explaining the present invention in detail, the dihalogenotin phthalocyanine used in the present invention is preferably dichlorotin phthalocyanine. Further, in the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 °) 8.4
°, 12.2 °, 13.8 °, 19.1 °, 22.4
Dihalogenotin phthalocyanine showing major diffraction peaks at °, 28.2 °, and 30.0 ° is preferable.

An example of the powder X-ray spectrum of the dihalogenotin phthalocyanine used is shown in FIG. As shown, Bragg angle (2θ ± 0.2 °) 8.4 °, 12.2 °, 1
The diffraction peaks at 3.8 °, 19.1 °, 22.4 °, 28.2 °, and 30.0 ° are the main peaks, and these intensity ratios or other than these peaks are variously varied depending on the detailed conditions. The method for producing the dihalogenotin phthalocyanine used in the present invention is not particularly limited, but for example, it is produced by the following method.

[0010]

[Chemical 1]

(In the above reaction formula, X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an allyloxy group, a nitro group, a cyano group, a hydroxyl group, a penzyloxy group or a halogen atom, Y represents a halogen atom, and l represents Represents an integer of 2, 3 or 4, m represents an integer of 0 to 4, and represents the number of substituents X on the benzene ring.)

As the organic solvent, quinoline, α-chloronaphthalene, β-chloronaphthalene, α-methylnaphthalene, methoxynaphthalene, diphenyl ether, diphenylmethane, diphenylethane, ethylene glycol, dialkyl ether, higher aliphatic amine, etc. An active high boiling organic solvent is desirable, the reaction temperature is usually 1
50-300 degreeC is desirable. In some cases, the reaction proceeds even if the solvent is not used and the temperature is raised to 160 ° C. or higher.

A crude product of a dihalogenotin phthalocyanine compound can be produced according to the above reaction scheme. As known phthalonitriles as raw materials, o-dicarboxylic acids, phthalic anhydrides, phthalimides, phthalic diamides and the like can be used as raw materials. Purification of the crude dihalogenotin phthalocyanine compound obtained as described above is carried out by sublimation purification, recrystallization purification, organic solvent treatment, thermal suspension purification with a high boiling point organic solvent, and sulfuric acid dissolution It can be performed according to a known method such as a reprecipitation method or an alkali washing method.

Organic solvents used for purification and thermal suspension purification during purification include xylene, naphthalene, toluene, monochlorobenzene, trichlorobenzene, o-dichlorobenzene, chloroform, tetrachloroethane, α- and β-chloronaphthalene. , Α- and β-methylnaphthalene, α-methoxynaphthalene, acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and other organic solvents used in the above reaction, water, methanol , Ethanol, propanol, butanol, pyridine, acetone,
Although an organic solvent such as methyl ethyl ketone or tetrahydrofuran can be used, a high boiling point organic solvent is particularly preferable for the hot suspension purification.

On the other hand, 1-used as a charge transport material
The pyrene carbaldehyde hydrazones are hydrazones having a structure obtained by reacting 1-pyrene carbaldehyde with a hydrazone derivative, and have the following general formula [I]

[0016]

[Chemical 2]

(Wherein R ¹ represents an alkyl group, an alkyl group, an aryl group or an aralkyl group, R ² represents a phenyl group which may have a substituent, or R ¹ and R ² represent Together

[0018]

[Chemical 3]

In the formula, R ¹ represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an allyl group; an aryl group such as a phenyl group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group; R ² is an o-tolyl group,
m-tolyl group, p-tolyl group, p-ethylphenyl group,
Substituted with a substituent such as o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, p-bromophenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group Represents a phenyl group.

Examples of the hydrazone compound include 1-pyrenecarbaldehyde, benzene, toluene, chlorobenzene, alcohol, acetone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran,
In an organic solvent inert to the reaction such as dioxane, depending on the case, p-toluenesulfonic acid, benzenesulfonic acid,
In the presence of a reaction accelerator such as hydrochloric acid, sulfuric acid, potassium acetate or sodium acetate, the following general formula [II]

[0021]

[Chemical 4]

(Wherein R ¹ and R ² have the same meanings as described above) and hydrazine or its hydrochloride or sulfate and 10 to 200 ° C., preferably 20
It is obtained by reacting under a temperature condition of -100 ° C. In addition, 1-pyrenecarbaldehyde and the following general formula [III]

[0023]

[Chemical 5]

(Wherein R ² has the same meaning as described above) and hydrazine represented by benzene, toluene,
Chlorbenzene, alcohol, acetone, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dioxane, etc. which are inactive in the reaction in an organic solvent,
Depending on the case, by reacting in the presence of a reaction accelerator such as p-toluenesulfonic acid, benzenesulfonic acid, hydrochloric acid, sulfuric acid, potassium acetate, sodium acetate, the following general formula [IV]

[0025]

[Chemical 6]

(Wherein R ² has the same meaning as described above), and a hydrazone represented by the following formula [V] is prepared.

[0027]

[Chemical 7] R ³ -Y ... [V]

(In the formula, R ³ represents an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; an allyl group; an aralkyl group such as a benzyl group and a phenethyl group, and Y represents a chlorine atom, a bromine atom and an iodine group. An alkylating agent, an allylating agent or an aralkylating agent represented by a halogen atom such as an atom) is used for reaction of tetrahydrofuran, dioxane, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and the like. In an active organic solvent, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine,
It can be produced by reacting at 10 to 200 ° C, preferably 20 to 100 ° C in the presence of a deoxidizing agent such as trimethylpentylammonium hydroxide.

The photoconductor of the present invention will be described in more detail. The photoconductor of the present invention is usually a laminate type photoconductor in which a charge generation layer and a charge transport layer are laminated. In this case, at least a conductive support is used. And a charge generation layer and a charge transport layer.
The charge generation layer and the charge transport layer usually have a structure in which the charge transport layer is laminated on the charge generation layer, but they may have the opposite structure. Further, it may be a single-layer type photoreceptor in which a charge generating material and a charge transporting material are dispersed and dissolved in a binder and applied on a conductive support.

In addition to these, an intermediate layer such as an adhesive layer or a blocking layer, or a protective layer or the like may be provided for improving electrical properties and mechanical properties.

As the conductive support, any of those known in electrophotographic photoreceptors can be used. Specific examples thereof include metal drums such as aluminum, stainless steel, and copper, sheets, laminates of these metal foils, and vapor-deposited materials. Further, there may be mentioned plastic films, plastic drums, papers, paper tubes, etc. which have been subjected to a conductive treatment by coating a conductive material such as metal powder, carbon black, copper iodide, and a polymer electrolyte with a suitable binder. In addition, a conductive plastic sheet or drum containing a conductive substance such as metal powder, carbon black or carbon fiber can be used.

Further, there may be mentioned a plastic film or belt which has been subjected to a conductive treatment with a conductive metal oxide such as tin oxide or indium oxide. The charge generation layer formed on these conductive supports is prepared by dissolving or dispersing the dihalogenotin phthalocyanine particles of the present invention, the binder polymer and, if necessary, the organic photoconductive compound, dye, electron withdrawing compound, etc. in a solvent. It is obtained by coating and drying the coating liquid obtained as described above. As the binder, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl alcohol and ethyl vinyl ether, polyvinyl acetal, polycarbonate, polyester, polyamide, polyurethane, cellulose ester. , Cellulose ether, phenoxy resin, silicon resin, epoxy resin and the like.
The ratio of the dihalogenotin phthalocyanine to the binder polymer is not particularly limited, but generally 5 to 500 parts by weight, preferably 20 to 300 parts by weight of the binder polymer is used with respect to 100 parts by weight of the dihalogenotin phthalocyanine. To do. A charge generating material other than dihalogenotin phthalocyanine can be used in combination, and in this case, the amount of dihalogenotin phthalocyanine used is reduced accordingly.

The thickness of the charge generation layer is 0.05 to 5 μm,
The thickness is preferably 0.1 to 2 μm. The charge transport layer into which charge carriers are injected from the charge generation layer contains a charge transport material having high carrier injection efficiency and transfer efficiency.

A binder polymer is optionally used in the charge transport layer. The binder polymer is preferably a polymer which has good compatibility with the above-mentioned charge transporting material and does not crystallize the charge transporting material after the formation of a coating film or undergo phase separation.Examples thereof include styrene, vinyl acetate and chloride. Vinyl, acrylic acid ester, methacrylic acid ester, polymers and copolymers of vinyl compounds such as butadiene, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose ester, cellulose ether, phenoxy resin, silicon resin, An epoxy resin etc. are mentioned.

The amount of the binder polymer used is usually 50 to 3000 parts by weight, preferably 70 to 1000 parts by weight, based on 100 parts by weight of the charge transport material. In addition to the above, various additives for improving the mechanical strength and durability of the coating film can be used in the charge transport layer. Examples of such additives include known plasticizers, various stabilizers, fluidity imparting agents, cross-linking agents and the like.

[0036]

The electrophotographic photosensitive member of the present invention thus obtained has high sensitivity, low residual potential and high charging property, and has little fluctuation due to repetition. Since it has good properties, it can be used as a highly durable photoreceptor. Further, it has a high sensitivity in the region of 750 to 850 nm, and thus is particularly suitable for a photoconductor for a semiconductor laser printer.

[0037]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, “parts” in Manufacturing Examples and Examples means “parts by weight”.

Production Example 1 25.0 parts of phthalodinitrile and 12.7 parts of SnCl ₄ were charged into 160 parts of α-chloronaphthalene and dissolved at 120 ° C. Then, the reaction temperature is gradually raised to 210
Heating and stirring was continued at 3.5 ° C. for 3.5 hours. After completion of the reaction, the mixture was allowed to cool, and hot filtered when the temperature of the reaction system fell to 100 ° C,
Then, heat suspension in methanol, boiling suspension in hot water, and heat suspension with N-methylpyrrolidone at 150 ° C for 2 hours, followed by hot filtration, hot suspension with methanol, filtration, and drying under reduced pressure to give a blue color. 10 parts of powder (compound No. 1) was obtained.

Compound No. The elemental analysis values of 1 were as follows. No. As 1 PcSnCl ₂

Table 1 C% H% N% Cl% Calculated value 54.70 2.28 15.95 9.97 Measured value 54.88 2.41 16.13 10.01

The results of infrared absorption spectrum measurement were the same as those shown in FIG. 1 of JP-A No. 62-119547. From the results of elemental analysis and measurement of infrared absorption spectrum, the tin phthalocyanine compound obtained in Production Example 1 had P
It was found to be cSnCl ₂ .

The measurement results of the powder X-ray diffraction were as shown in FIG. In the same manner as in Production Example 1, the compound Nos. 2-11 dihalogenotin phthalocyanines were synthesized.

[0042]

[Chemical 8]

[0043]

[Table 2] Table 1 Compound No. X m Y 2 -H 0 F 3 -H 0 I 4 -H 0 Br 5 —CH ₃ 1 Cl 6 —OH 1 Cl 7 3-NO ₂ 1 Cl 8 —OCH ₃ 4 Cl 9 Cl 4 Cl 10 -OCH ₂ -C ₆ H ₅ 4 Cl 11 -CN 1 Cl

Example 1 Compound No. 1 produced in Production Example 1 0.4 g of dichlorotin phthalocyanine of 1 and 0.2 g of polyvinyl butyral together with 30 g of 4-methoxy-4-methyl-2-pentanone were dispersed with a sand grinder, and this dispersion was vapor-deposited on a polyester film on an aluminum vapor-deposited layer. Was coated with a film applicator to a dry film thickness of 0.3 g / m ² and dried to form a charge generation layer.

On the charge generation layer, 90 parts of 1-pyrenecarbaldehydediphenylhydrazone, a polycarbonate resin (Mitsubishi Gas Chemical Co., Inc., Iupilon E-2000)
A charge transport layer having a film thickness of 17 μm consisting of 100 parts is laminated,
An electrophotographic photoreceptor having a laminated photosensitive layer was obtained.

As the sensitivity of this photoreceptor, the half-exposure amount (E ¹
/ ₂ ) is an electrostatic copying paper tester (Model S of Kawaguchi Denki Seisakusho)
P-428). That is, the photoreceptor was negatively charged by corona discharge by an applied voltage set so that the corona current was 50 μA in the dark. Then from a white light with an illuminance of 20 lux 775 nm using a filter
Of light (corresponding to illuminance 2.4Lux) was removed, 1 where the surface potential is exposed by this light to determine the exposure amount required for half the -250V from -500V (E _^1/2).
It was 58lux · sec.

Charge voltage of the photoconductor at this time (initial surface potential)
Was −711 V and the surface potential (residual potential) after 10 seconds of exposure was −17 V.

Example 2 Instead of the dichlorotin phthalocyanine used in Example 1, compound No. A charge generation layer was prepared in the same manner as in Example 1 except that the dihalogenotin aphthalocyanine of Example 2 was used, and the charge transport material used in Example 1 was used in Example 1
When a photoconductor was prepared according to the method of 1. and the sensitivity was measured by the same method as in Example 1, it was 2.1 lux · sec.

Example 3 Instead of 1-pyrenecarbaldehydediphenylhydrazone used in Example 1, the following general formula [I] was used.

[0050]

[Chemical 9]

Using the hydrazones represented by, a photoconductor was prepared according to the method of Example 1, and the sensitivity was measured in the same manner as in Example 1. The results are shown in Tables 2 and 3. ..

[0052]

[Table 3] Table-2 Examples represented by the general formula [I] Example 1-Pyrenecarbaldehyde dehydration half-exposure Dorazones (lux · sec) R ¹ R ² 3-1 -CH ₃ -C ₆ H ₅ 1. _{8 3-2 -C 2 H 5 -C 6} H 5 1.9 3-3 -CH-CH = CH 2 -C 6 H 5 2.1 3-4 -CH 2 -C 6 H 5 -C 6 H ₅ 1.8 3-5 -C ₄ H ₉ (n) _{-C 6 H 5 2.1 3-6 -C 3} H 7 (iso) -C ₆ H ₄ -Cl 2.8 (Attached in the _{para-position) 3-7 -C 2 H 5 -C 6} H 4 -C 2 H 5 2.3 (Attached in the _{para-position) 3-8 -C 10 H 7 -C 6} H 4 -Br 2.2 (Join at 1st position) (Attached at the para _{position) 3-9 -CH-CH = CH 2} -C 6 H 4 -CH 3 2.1 (Attached in the _{meta) 3-10 -CH-CH = CH 2} -C 6 H 4 -OCH 3 2.6 (Binding at para position) 3-11 -CH ₃ -C ₆ H ₄ -CH ₃ 2.3 (Bonding at the ortho position) 3-12 -C ₂ H ₅ -C ₆ H ₄ -OCH ₃ 2.1 (Bonded at meta position)

[0053]

[Table 4]

[Brief description of drawings]

FIG. 1 is a powder X-ray diffraction spectrum diagram of dichlorotin phthalocyanine used in the present invention.

Claims (1)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer containing a charge generation material and a charge transport material on a conductive finger carrier, wherein dihalogenotin phthalocyanine is used as the charge generation material and 1- An electrophotographic photoreceptor characterized by using pyrene carbaldehyde hydrazones.