JP2595527B2 - Photoconductor - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member having a photosensitive layer containing a styryl compound as a main component.

Conventional Technology and Problems Electrophotographic photoreceptors include a function-separated type in which a charge generation layer and a charge transport layer are laminated on a conductive support, and a photoconductive layer in which photoconductive particles are dispersed in a resin. A dispersion type formed on a support is widely known.

In the function-separated type, the basic functions of the photoreceptor, that is, the generation and transport of charge carriers, are shared by separate substances, resulting in high surface potential, high charge retention, high photosensitivity, and stable repetition characteristics. A photosensitive layer can be obtained. It is known that a large number of compounds are both effective as charge-generating materials for charge generation and charge-transporting materials for charge transport of a function-separated type. For example, many charge transport layers using a low-molecular organic photoconductor have been proposed. However, the one using 2,5-bis (p-diethylaminophenyl) -1,3,4-osisadiazole described in U.S. Pat. No. 3,189,447 has low compatibility with the binder, and crystal Easy to precipitate. Also,
The one using the diarylalkane derivative described in U.S. Pat.No. 3,820,989 has good compatibility with the binder, but has a sensitivity change when used repeatedly, and still has initial sensitivity and residual potential. There are points to be greatly improved in characteristics, sensitivity change and durability when repeatedly used.

Means for Solving the Problems An object of the present invention is to provide an electrophotographic photoreceptor which solves the above-mentioned conventional disadvantages, has high photosensitivity, and has stable electrophotographic characteristics even after repeated use. .

That is, the gist of the present invention is the following general formula [I]: [Wherein, R ₁ is a cyano group or a halogen atom, Ar ₁ is an aryl group which may have a substituent, Ar ₂ and Ar ₃ are each independently an aromatic hydrocarbon which may have a substituent. Or an aromatic heterocyclic group.

An electrophotographic photosensitive member containing a styryl compound represented by the formula:

In the present invention, the styryl compound represented by the general formula [I] is used as a photoconductive substance of a photoreceptor, or only the excellent charge transporting ability of the styryl compound of the present invention is used to convert the styryl compound into a functionally separated type. Use in the charge transport layer of the electrophotographic photoreceptor, excellent film properties, excellent electrophotographic properties such as charge retention ability, sensitivity and residual potential, and stable characteristics with little fatigue deterioration when used repeatedly. An electrophotographic photoreceptor capable of exhibiting the above characteristics can be produced.

Preferred specific examples of the styryl compound represented by the general formula [I] of the present invention include, for example, those having the following structural formulas, but are not limited thereto.

The styryl compound represented by the general formula [I] is, for example, represented by the following general formula [II]: [Wherein, R ₁ and Ar ₁ have the same meanings as [I], and R ₂ and R _{3 each} represent an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group that forms a phosnium salt. A phosphorus compound represented by the following general formula [III]: [Wherein, Ar ₂ and Ar ₃ have the same meanings as [I]] can be obtained by condensation with an acrolein compound represented by the following formula: Of the phosphorus compound represented by the general formula [II]
R ₁ and R ₂ are particularly preferably a cyclohexyl group, a benzyl group, a phenyl group or a lower alkyl group.

As the reaction solvent in the above method, for example, hydrocarbons, alcohols, ethers are good, methanol,
Ethanol, isopropanol, butanol, 2-methoxyethanol, 1,2-dimethoxyethane, bis (2-
Methoxyethyl) ether, dioxane, tetrahydrofuran, toluene, xylene dimethyl sulfoxide, N,
N-dimethylformamide, N-methylpyrrolidone, 1,3
-Dimethyl-2-imidazolidinone and the like.
Among them, polar solvents such as N, N-dimethylformamide and dimethylsulfoxide are preferred.

Examples of the condensing agent include sodium hydroxide, potassium hydroxide, sodium amide, sodium hydrogen and sodium methylate, and alcoholates such as potassium-t-butoxy.

The reaction temperature can be selected over a wide range from about 0 ° C to about 100 ° C. Preferably it is 10 to 80 degreeC.

The compound [II] used according to the present invention uses a corresponding quaternary phosphonium salt, for example, a triphenylphosphonium salt, instead of a phosphorus compound, and is used in Wittig.
It is obtained by condensing with an aldehyde compound [III] via the phosphorylene step by the method of ig). These styryl compounds may be used alone or as a mixture.

Examples of the constitution of an electrophotographic photosensitive member using the styryl compound of the present invention are schematically shown in FIGS.

FIG. 1 shows a photoconductor in which a photoconductor (4) in which a photoconductive material (3) and a charge transport material (2) are mixed with a binder is formed on a substrate (1). The styryl compounds of the present invention have been used.

FIG. 2 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as a photosensitive layer. The charge transport layer (5) is formed on the surface of the charge generation layer (6). I have. The charge transport layer (5) contains the styryl compound of the present invention.

FIG. 3 shows a function-separated type photoreceptor having a charge generation layer (6) and a charge transport layer (5) as in FIG. 2, but the surface of the charge transport layer (5) is opposite to FIG. A charge generation layer is formed.

FIG. 4 shows that the surface protective layer (7) is further provided on the surface of the photoreceptor of FIG. 1, and the photosensitive layer (4) is separated into a charge generation layer (6) and a charge transport layer (5). It may be a function separated type.

FIG. 5 shows that an intermediate layer (8) is provided between the substrate (1) and the photosensitive layer (4). The intermediate layer (8) improves the adhesiveness, the coating property, and protects the substrate. It can be provided for improving the charge injection property from the base to the photoconductive layer. As the intermediate layer, a polyimide resin, a polyester resin, a polyvinyl butyral resin, casein, or the like may be used. In the photoconductor of this embodiment, the photosensitive layer may be of a function-separated type.

The electrophotographic photoreceptor of the present invention comprises a styryl compound represented by the general formula [I] dissolved and dispersed in a suitable solvent together with a binder, and if necessary, a photoconductive material and an electron withdrawing compound, or a sensitizing infection. A coating solution obtained by adding a pigment and other pigments is coated on a conductive substrate, and dried,
It can be produced by forming a photosensitive layer having a thickness of from 30 to 30 μm, preferably from 6 to 20 μm.

Specifically, the charge separation layer and the charge transport layer are laminated on the conductive support, and the function-separated type photosensitive member having the same configuration as the photosensitive member in FIG. Vacuum deposition of the charge generation material, or, if necessary, an appropriate solvent or, if necessary, a coating solution prepared by dispersing in a solution in which a binder resin is dissolved, and drying to form a charge generation layer,
A solution obtained by dissolving a styryl compound and a binder resin as a charge transport material in a suitable solvent is applied thereon and dried to form a charge transport layer. In the case of performing vacuum deposition, phthalocyanines such as metal-free phthalocyanine, titanyl phthalocyanine, and aluminum chlorophthalocyanine are used. When dispersing, for example, a disazo pigment is used. At this time, the thickness of the charge generation layer is 4 μm or less, preferably 2 μm or less, and the thickness of the charge transport layer is 3 to 30 μm, preferably 5 to 20 μm. The ratio of the styryl compound in the charge transport layer is from 0.02 to 2 parts by weight, preferably from 0.03 to 2 parts by weight, per part by weight of the binder resin.
Preferably it is 1.3 parts by weight. Further, another charge transport material may be combined. In the case of a polymer charge transporting material that can be used as a binder itself, other binders may not be used. The configuration of the photoreceptor is the third
Similarly to the photoreceptor shown in the figure, a configuration in which a charge transport layer is formed on a conductive support and a charge generation layer is laminated thereon may be employed.

The dispersion type photoreceptor having a photoconductive layer formed on a conductive support and having the same configuration as the photoreceptor of FIG. 1 described above is obtained by dissolving fine particles of a photoconductive material in a styryl compound and a binder resin. It is obtained by dispersing in a solution, applying this on a conductive support, and drying to form a photoconductive layer. At this time, the thickness of the photoconductive layer is 3 to 30 μm, preferably 5 to 20 μm.
m is good. If the amount of the photoconductive material to be used is too small, the sensitivity is poor, and if it is too large, the chargeability is deteriorated, or the strength of the photoconductive layer is weakened, and the amount of the photoconductive material in the photoconductive layer is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight per 1 part by weight of the resin, and the ratio of the styryl compound is 0.01 to 2 parts by weight, preferably 0.02 to 1.
2. Weight parts are preferred. Further, it may be used in combination with a polymer photoconductor such as polyvinyl carbazole which can be used as a binder by itself. Further, it may be combined with another charge transporting material, for example, a hydrazone compound.

The charge generating material in the function separation type of the electrophotographic photoreceptor of the present invention and the photoconductive material in the dispersion type are bisazo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, and cyanine. Pigments, styryl pigments, pyrylium pigments, azo pigments, quinacridone pigments, indico pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indathrone pigments, squarylium pigments,
Organic substances such as phthalocyanine pigments and selenium
Examples include inorganic substances such as tellurium, selenium / arsenic, cadmium sulfide, and amorphous silicon. Any other material that absorbs light and generates charge carriers with extremely high efficiency can be used.

Those usable as binders are electrically insulating, and any of thermoplastic resins, thermosetting resins, photocurable resins, and photoconductive resins known per se can be used. Examples of suitable binder resins include, but are not limited to, saturated polyester resins, polyamide resins, acrylic resins, ethylene-vinyl acetate copolymers, ionically crosslinked olefin copolymers (ionomers),
Thermoplastic binders such as styrene-butadiene block copolymer, polyarylate, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, styrene resin; epoxy resin, urethane resin, silicone resin, phenol resin, melamine Thermosetting binders such as resins, xylene resins, alkyd resins, and thermosetting acrylic resins; photocurable resins; photoconductive resins such as poly-N-vinylcarbazole, polyvinylpyrene, and polyvinylanthracene. These can be used alone or in combination. It is desirable that these electrically insulating resins have a volume resistance of 1 × 10 ¹² Ω · cm or more when measured alone. More preferred are polyester resin, polycarbonate and acrylic resin.

The electrophotographic photoreceptor of the present invention, together with a binder, halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate, a plasticizer such as o-terphenyl, chloranil, tetracyanoethylene, 2,4,7
Electron-withdrawing sensitizers such as trinitro-9-fluorenone, 5,6-dicyanobenzoquinone, tetracyanoquinodimethane, tetrachlorophthalic anhydride, 3,5-dinitrobenzoic acid, methyl violet, rhodamine B, cyanine dye, A sensitizer such as a pyrylium salt or a thiapyrylium salt may be used.

The electrophotographic photoreceptor thus formed may have an adhesive, an intermediate layer, and a surface protective layer as necessary, as shown in FIGS. 4 and 5 described above.

As a material used for the intermediate layer, polyimide, polyamide, nitrocellulose, polyvinyl butyral, a polymer such as polyvinyl alcohol as it is, or a dispersion of a low-resistance compound such as tin oxide or indium oxide, aluminum oxide, zinc oxide, A deposited film of silicon oxide or the like is suitable.

 The thickness of the intermediate layer is desirably 1 μm or less.

As a material used for the surface protective layer, a polymer such as an acrylic resin, a polyaryl resin, a polycarbonate resin, or a urethane resin as it is, or a material in which a low-resistance compound such as tin oxide or indium oxide is dispersed is appropriate. . Also, an organic plasma polymerized film can be used. The organic plasma polymerized film is appropriately oxygen if necessary,
It may contain nitrogen, halogen, atoms of groups III and V of the periodic table.

 The thickness of the surface protective layer is desirably 5 μm or less.

As described above, the styryl compound of the present invention can be easily produced, and a photoreceptor containing the same can be used as a function-separated type or a dispersed type, and can be combined with various charge generating materials and binder resins. Optionally, other charge transport materials can be added. Therefore, the electrophotographic photoreceptor containing the styryl compound of the present invention is extremely easy to manufacture and has a wide range of use, and has excellent repetition characteristics by preventing photo-fatigue by the styryl compound, improving sensitivity and improving surface potential change. Less.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Synthesis Example (Compound [3]) And 2.53 g of a phosphonate represented by the following formula: Dissolve 3.60 g of the aldehyde compound represented by in 30 ml of dimethylformamide and, while heating to 30 to 40 ° C, 5 g of potassium-ter-butoxide in 70 ml of dimethylformamide.
Was added dropwise. Then, after stirring at room temperature for 8 hours, the mixture was left overnight. The obtained mixture was added to 900 ml of ice water, neutralized with dilute hydrochloric acid, and after about 30 minutes, the precipitated crystals were filtered. The filtered product was linearized with water and further purified by recrystallization using acetonitrile to obtain 3.7 g of yellow needle crystals.
(Yield: 82%) The elemental analysis is as follows.

Example 1 Disazo compound represented by the following general formula (A) 0.45 parts of a polyester resin (Vylon 200 manufactured by Toyobo Co., Ltd.) and 0.45 parts of the resin were dispersed together with 50 parts of cyclohexanone by a sand grinder. The obtained dispersion of the disazo compound was applied on a 100-μm-thick aluminized mylar using a film applicator so that the dry film thickness became 0.3 g / m ^2, and then dried. 70 parts of a styryl compound [2] and 70 parts of a polycarbonate resin (K-1300 manufactured by Teijin Chemicals Ltd.)
A solution dissolved in 400 parts of 1,4-dioxane has a dry film thickness of 16 μm.
m to form a charge transport layer. Thus, an electrophotographic photosensitive member having a two-layer photosensitive layer was obtained.

The photoreceptor thus obtained was corona-charged at −6 KV using a commercially available electrophotographic copying machine (EP-470Z manufactured by Minolta Camera Co., Ltd.), and the initial surface potential V ₀ (V) and the initial potential were halved. exposure _{E 1/2 (lux · sec} ) taken to, it was measured decay rate of the initial potential when left in a second dark DDR ₁ (%).

Examples 2 to 4 In the same manner as in Example 1, the same configuration was used, except that styryl compounds [3], [4], and [6] were used instead of styryl compound [2] used in Example 1. A photoreceptor was produced.

The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1.

Example 5 Disazo compound represented by the following general formula (B) 0.45 part and 0.45 part of a polystyrene resin (molecular weight: 40,000) were dispersed together with 50 parts of cyclohexanone by a sand grinder. Dispersion of the resulting disazo compound to a thickness of 10
Using a film applicator on a 0-μm aluminized mylar using a film applicator, the film was applied so as to have a dry film thickness of 0.3 g / m ² and then dried. On the charge generation layer thus obtained, 70 parts of a styryl compound [10] and a polyarylate resin (U
A solution in which 70 parts of -100 (manufactured by Unitika Ltd.) was dissolved in 400 parts of 1,4-dioxane was applied to a dry film thickness of 16 μm to form a charge transport layer. Thus, an electrophotographic photoreceptor having a two-layer photosensitive layer was produced.

Examples 6 to 8 In the same manner as in Example 5, the same configuration was used, except that styryl compounds [11], [17], and [21] were used instead of styryl compound [10] used in Example 5. A photoreceptor was produced.

The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 1.

Example 9 Copper phthalocyanine (50 parts) and tetranitro copper phthalocyanine (0.2 parts) were dissolved in 98% concentrated sulfuric acid (500 parts) with sufficient stirring and dissolved in water (5,000 parts) to prepare a photoconductive material composition of copper phthalocyanine and tetranitro copper phthalocyanine. After the precipitation, the precipitate was filtered, washed with water, and dried at 120 ° C. under reduced pressure.

10 parts of the photoconductive composition thus obtained was mixed with a thermosetting acrylic resin (Acrydic A405; manufactured by Dainippon Ink Co., Ltd.) 2
2.5 parts, melamine resin (Super Beckamine J820; manufactured by Dainippon Ink Co., Ltd.) 7.5 parts, styryl compound [2
1] 15 parts were put in a ball mill pot together with 100 parts of a mixed solvent obtained by mixing methyl ethyl ketone and xylene in the same amount, and dispersed for 48 hours to prepare a photosensitive coating solution. The coating solution was applied on an aluminum substrate and dried. Then, a photosensitive layer having a thickness of about 15 μm was formed to produce a photosensitive member.

The thus obtained photosensitive member, the same method as that in Example 1, except V ₀ and subjected to corona charging at _{+ 6KV, E 1/2,} DDR
₁ was measured.

Examples 10 to 12 In the same manner as in Example 9, having the same constitution, except that styryl compounds [22], [27] and [28] are used instead of styryl compound [21] used in Example 9 A photoreceptor was produced.

The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 9.

Comparative Examples 1 to 4 In the same manner as in Example 9 and having the same constitution, except that the styryl compound [21] used in Example 9 was replaced with the following compounds (C), (D), (E) and (F) A photosensitive member was produced in the same manner as in Example 9 except that each of the above was used.

The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 9.

Comparative Examples 5 to 7 In the same manner as in Example 9 and having the same constitution, except that the following styryl compounds (G), (H) and (I) were used instead of the styryl compound [21] used in Example 9 A photoconductor was prepared in the same manner as in Example 9 except for using the same.

The thus obtained photosensitive member was measured _{V 0, E 1/2,} DDR 1 in the same manner as in Example 9.

V _{0 of} the photoreceptors obtained in Examples 1 to 12 and Comparative Examples 1 to 8,
The measurement results of the E _1/2, DDR ₁ are summarized in Table 1.

As can be seen from Table 1, the photoreceptor of the present invention has a sufficient charge retention ability in both a lamination type and a single layer type, has a small dark decay rate as a photoreceptor can be sufficiently used, and has excellent sensitivity. Is clear from the data.

Further, a repetitive real-photographing test was performed on a photoconductor of Example 9 with a commercially available electrophotographic copying machine (EP-350Z manufactured by Minolta Camera Co., Ltd.) at the time of positive charging. In the final image, a clear image was obtained with excellent gradation and no change in sensitivity, and it was found that the photoreceptor of the present invention had stable repetition characteristics.

Effect of the Invention The photoreceptor of the present invention, by containing the above styryl compound, is excellent in charge transportability, has a stable initial surface potential, has a sufficiently small dark decay rate, and has good chargeability. Have. In addition, there is little carrier trapping, high sensitivity, and little light fatigue.

The electrophotographic photoreceptor obtained by using the compound of the present invention can effectively suppress light fatigue, reduce the surface potential and increase the residual potential, reduce the change in sensitivity when used repeatedly, and stabilize the electrophotographic characteristics. And high sensitivity,
A clear image can be obtained.

In addition, styryl compounds are particularly effective as charge transport materials for function-separated photoconductors.

[Brief description of the drawings]

FIGS. 1 to 5 are schematic views of a photoreceptor according to the present invention. FIGS. 1, 4, and 5 show a dispersion type photoreceptor obtained by laminating a photosensitive layer on a conductive support. 2 and 3 show the structure of a function-separated type photoconductor in which a charge generation layer and a charge transport layer are laminated on a conductive support. DESCRIPTION OF SYMBOLS 1 ... Conductive support, 2 ... Charge transport material 3 ... Photoconductive material, 4 ... Photosensitive layer 5 ... Charge transport layer, 6 ... Photoconductive layer 7 ... Surface protective layer, 8 ... Middle class

Claims (1)

(57) [Claims] 1. A photoreceptor comprising a styryl compound represented by the following general formula [I]: [Wherein, R ₁ is a cyano group or a halogen atom, Ar ₁ is an aryl group which may have a substituent, Ar ₂ and Ar ₃ are each independently an aromatic hydrocarbon which may have a substituent. Or an aromatic heterocyclic group.