JP2002003468A - Sulfur-containing amine compound and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor having high sensitivity and high durability by using a new sulfur-containing amine compound as a charge transfer substance. SOLUTION: In this electrophotographic photoreceptor, a photosensitive layer laid on an electroconductive substrate is constituted of a laminate of a charge production layer containing a charge production substance and a charge transfer layer comprising a charge transfer substance containing the sulfur-containing amine compound represented by general formula (I) (Ar1 is a substitutable aryl group or a substitutable heterocyclic group; Ar2 is a substitutable arylene group or a substitutable bifunctional heterocyclic group; Ar3 is an aryl group which may contain a substituent group, a heterocyclic group which may contain a substituent group, an aralkyl group which may contain a substituent group, a 1-5C alkyl group which may contain a substituent group, a 1-5C fluoroalkyl group which may contain a substituent group or a 1-5C perfluoroalkyl group which may contain a substituent group; and (n) is an integer of 1-3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member containing a sulfur-containing amine compound in a photosensitive layer.

[0002]

2. Description of the Related Art In recent years, electrophotographic technology is used not only in the field of copiers but also in the field of various types of printers, since it can provide high-quality images with immediacy. I have.

In the field of electrophotographic photoreceptors (hereinafter, also simply referred to as "photoreceptors") used in the electrophotographic technology, as photoconductive materials, selenium, arsenic, selenium alloys, selenium-tellurium alloys, sulfides Inorganic materials such as cadmium and zinc oxide have been used. However, in recent years, instead of such inorganic materials, an organic photoreceptor mainly composed of an organic photoconductive material having advantages such as no pollution, good film formability and ease of production has been developed. It became so.

Among the organic photoconductors, a so-called stacked type photoconductor in which a charge generation layer composed of a charge generation material and a charge transport layer composed of a charge transfer material are sequentially laminated has been devised. It has become mainstream. That is, in the case of a stacked photoreceptor, by combining an efficient charge generating substance and a charge transfer substance, 1) a photoreceptor having higher sensitivity can be obtained, and 2) a material selection range is wide and a highly safe photoreceptor can be obtained. Photoreceptors are the mainstream in terms of their ability to obtain a body, and 3) their high coating productivity and relatively low cost. Further, the printing durability has been put into practical use to a copying machine having high printing durability with a total number of copies of 200,000 or more and high speed performance with a copying speed of 70 or more per minute.

As described above, some of the organic laminated photoconductors that have been put into practical use so far have excellent performance, but most of them are related to photoconductor production in pursuit of the performance. At present, various problems still exist.

Here, among those specific problems,
Some of those related to charge transfer materials are listed as follows: 1) low compatibility with the binder, 2) easy precipitation of crystals, 3) change in sensitivity when used repeatedly, 4) chargeability and Poor repetition characteristics; and 5) poor residual potential characteristics.

[0007] Focusing on the development of such charge transfer materials, a typical one of them is classified according to its structural characteristics. A hydrazone system (JP-A-54-59143) having a central nucleus,
Stilbene-styryl type (JP-A-58-198043), triarylamine type (JP-B-58-3237)
No. 2) has been energetically studied. Then, a series of compounds having a monocyclic heterocyclic ring system at its central nucleus, phenothiazine, triazole, quinoxaline, oxadiazole, oxazole, pyrazoline, dihydronicotinamide compounds, indoline compounds and semicarbazones Compounds have been developed.
Recently, it has a fused polycyclic hydrocarbon system as its central nucleus,
Pyrene derivatives, naphthalene derivatives and terphenyl derivatives (JP-A-7-48324) have been developed.

[0008]

As described above, despite the fact that many organic compounds have been developed as charge transfer materials, none of the organic compounds satisfy all of the above-mentioned problems. Under the present circumstances, those which satisfy the basic properties as well as mechanical strength and high durability have not yet been sufficiently obtained.

It is an object of the present invention to provide a novel sulfur-containing amine compound having a thioether bond, and an electrophotographic photoreceptor having high sensitivity and high durability by using the compound as a charge transfer material.

[0010]

The present invention is a sulfur-containing amine compound represented by the following general formula (I).

[0011]

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[0012] (wherein, Ar ¹ is .Ar ² good arylene group or a substituted also contain substituents represented a heterocyclic group which may contain may contain a substituent aryl group or a substituted group Ar3 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, or an optionally substituted aralkyl group. A group, an alkyl group having 1 to 5 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent or a carbon atom which may have a substituent. Represents a perfluoroalkyl group of 1 to 5. n represents an integer of 1 to 3.)

According to the present invention, a novel sulfur-containing amine compound having a thioether bond can be provided.
The sulfur-containing amine compound represented by the general formula (I) has a wide conjugated system, has a high mobility by donating an electron of a sulfur atom, can improve the residual potential characteristics of the electrophotographic photoreceptor, Because it has excellent compatibility with the agent,
It can be used as a charge transfer material in an electrophotographic photoreceptor and can be contained in a large amount in a photosensitive layer to improve the photosensitivity of the electrophotographic photoreceptor. Thereby, an electrophotographic photoreceptor having high sensitivity and high durability can be provided.

According to the present invention, there is provided an electrophotographic photoreceptor wherein the photosensitive layer provided on the conductive support contains a sulfur-containing amine compound represented by the following general formula (I).

[0015]

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[0016] (wherein, Ar ¹ is .Ar ² good arylene group or a substituted also contain substituents represented a heterocyclic group which may contain may contain a substituent aryl group or a substituted group Ar3 represents an optionally substituted aryl group, an optionally substituted heterocyclic group, or an optionally substituted aralkyl group. A group, an alkyl group having 1 to 5 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent or a carbon atom which may have a substituent. Represents a perfluoroalkyl group of 1 to 5. n represents an integer of 1 to 3.)

According to the present invention, by using the sulfur-containing amine compound represented by the general formula (I) as a charge transfer material, the sulfur-containing amine compound has a wide conjugated system, and has an electron of a sulfur atom. The donor provides high mobility, improves the residual potential characteristics of the electrophotographic photoreceptor, and has excellent compatibility with the binder. Sensitivity can be improved. Thereby, an electrophotographic photoreceptor having high sensitivity and high durability can be provided.

Further, the present invention is characterized in that the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (II).

[0019]

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(Wherein, Ar ⁴ and Ar ⁵ represent an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, An alkyl group having 1 to 5 carbon atoms which may be contained, a fluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent or 1 to 5 carbon atoms which may contain a substituent
Represents a perfluoroalkyl group. Ar ¹ and Ar ² have the same meanings as those represented by formula (I). )

According to the present invention, by using the sulfur-containing amine compound represented by the general formula (II) as a charge transfer material, the sulfur-containing amine compound represented by the general formula (I) can be used similarly to the case of using the sulfur-containing amine compound represented by the general formula (I). An electrophotographic photosensitive member having high sensitivity and high durability can be provided.

Further, the present invention is characterized in that the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (III).

[0023]

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(Wherein a represents an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, and a substituent A perfluoroalkyl group having 1 to 5 carbon atoms, which may be
It represents an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and m represents an integer of 1 to 4. However, when m is 2 or more, each a may be the same or different, and may form a ring with each other.
Ar ¹ , Ar ⁴ and Ar ⁵ have the same meanings as those represented by formula (II). )

According to the present invention, by using the sulfur-containing amine compound represented by the general formula (III) as a charge transfer material, the sulfur-containing amine compound represented by the general formula (I) can be used similarly to the case of using the sulfur-containing amine compound represented by the general formula (I). An electrophotographic photosensitive member having high sensitivity and high durability can be provided.

Further, the present invention is characterized in that the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (IV).

[0027]

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(Wherein b, c and d are an alkyl group having 1 to 3 carbon atoms which may have a substituent, and a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent. A perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, k and j each represent an integer of 1 to 4, provided that when l, k and j are each 2 or more, b, c and d corresponding thereto may be the same or different;
They may form a ring with each other. a and m are represented by the general formula (II)
It has the same meaning as that shown in I). )

According to the present invention, by using the sulfur-containing amine compound represented by the general formula (IV) as a charge transfer material, the sulfur-containing amine compound represented by the general formula (I) can be used similarly to the case of using the sulfur-containing amine compound represented by the general formula (I). An electrophotographic photosensitive member having high sensitivity and high durability can be provided.

Further, the present invention is characterized in that the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (V).

[0031]

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(Wherein, e and f are an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, a substituent Represents a perfluoroalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, and i and h are each 1 And i is an integer of 4 or more, provided that when i and h are 2 or more, corresponding e and f may be the same or different, and may form a ring with each other.
b, m and l have the same meanings as those represented by formula (IV). )

According to the present invention, by using the sulfur-containing amine compound of the general formula (V) as a charge transfer material, high sensitivity and high sensitivity can be obtained as in the case of using the sulfur-containing amine compound of the general formula (I). An electrophotographic photosensitive member having high durability can be provided.

Further, the present invention is characterized in that the photosensitive layer has a laminated structure of a charge generation layer containing a charge generation material and a charge transfer layer containing a charge transfer material containing the sulfur-containing amine compound. I do.

According to the present invention, the sulfur-containing amine compound represented by the above general formula (I) is contained in the charge transfer layer as a charge transfer material, so that a function-separated type laminate having high sensitivity and high durability can be obtained. An electrophotographic photoreceptor can be provided.

Further, the present invention is characterized in that the photosensitive layer comprises a single layer containing a charge generating substance and a charge transfer substance containing the sulfur-containing amine compound.

According to the present invention, by containing the sulfur-containing amine compound represented by the general formula (I) as a charge transfer material in a single photosensitive layer together with a charge generation material,
A single-layer electrophotographic photosensitive member having high sensitivity and high durability can be provided.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic photoreceptor according to an embodiment of the present invention can employ various modes by using a sulfur-containing amine compound represented by the following general formula (I) as a charge transfer material. A structural example of the photoconductor is schematically shown below.

[0039]

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FIG. 1 shows a charge generation layer 5 on a conductive support 1.
FIG. 3 is a cross-sectional view schematically illustrating a photoconductor on which a charge transfer layer 6 is formed. As the photosensitive layer 4 on the conductive support 1, the charge generation layer 5 in which the charge generation material 2 is the main component dispersed in the binder and the charge transfer in which the charge transfer material 3 is the main component dispersed in the binder. This is a function-separated type photoconductor in which the layer 6 is laminated. The charge transfer layer 6 is formed on the surface of the charge generation layer 5, and the structure of the photoreceptor using the above-described sulfur-containing amine compound as the charge transfer substance 3 in the charge transfer layer 6 is shown.

FIG. 2 shows the charge transfer layer 6 on the conductive support 1.
FIG. 3 is a cross-sectional view schematically illustrating a photoconductor on which a charge generation layer 5 is formed. The same charge generation layer 5 and charge transfer layer 6 as in FIG.
1, the charge generation layer 5 is provided on the surface of the charge transfer layer
Is a function-separated type photoreceptor.

FIG. 3 is a cross-sectional view schematically showing a photosensitive member in which a photosensitive layer 14 containing a charge generating substance 2 and a charge transfer substance 3 is formed on a conductive support 1. The structure of a photoconductor composed of a single layer in which a charge generation material 2 and a charge transfer material 3 are dispersed in a binder as a photosensitive layer 14 on a conductive support 1 is shown.

FIG. 4 is a sectional view schematically showing a photoreceptor in which the surface protective layer 7 is provided on the photosensitive layer 14 of FIG. The surface protective layer 7 is formed on the conductive support 1 and the same photosensitive layer 14 as in FIG.
Is provided, and the structure of the photoconductor composed of the single-layer photosensitive layer 14 is shown.

FIG. 5 shows the conductive support 1 and the photosensitive layer 4 shown in FIG.
FIG. 3 is a cross-sectional view schematically showing a photoconductor provided with an intermediate layer 8 between the photoconductor and the photoconductor. The structure of a function-separated type photoconductor in which an intermediate layer 8 is provided between the conductive support 1 and the same photosensitive layer 4 as in FIG.

The sulfur-containing amine compound used as a charge transfer material in the photoreceptors having these various structures is represented by the general formula (I).

In the general formula (I), Ar ¹ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent.

Specific examples of Ar ¹ include phenyl,
And aryl groups such as tolyl, anisyl, naphthyl, pyrenyl and biphenyl, and heterocyclic groups such as benzofuryl, benzothiazolyl, benzoxazolyl and N-ethylcarbazolyl.

In the general formula (I), Ar ² represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.

Specific examples of Ar ² include phenylene, naphthylene, pyridylene and biphenylene groups.

In the general formula (I), Ar ³ represents an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, an aralkyl group optionally having a substituent, a substituent An alkyl group having 1 to 5 carbon atoms, which may contain
A fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent or 1 to 5 carbon atoms which may have a substituent;
5 represents a perfluoroalkyl group.

Specific examples of Ar ³ include phenyl,
Aryl groups such as tolyl, anisyl, naphthyl, pyrenyl and biphenyl; heterocyclic groups such as benzofuryl, benzothiazolyl, benzoxazolyl and N-ethylcarbazolyl; aralkyls such as benzyl, methylbenzyl, methoxybenzyl and 2-thienylmethyl Groups, alkyl groups such as methyl, ethyl and n-propyl, perfluoroalkyl groups such as trifluoromethyl, and fluoroalkyl groups such as 1,1,1-trifluoroethyl.

In the general formula (I), n is 1,2
Or 3 is indicated. In particular, among the sulfur-containing amine compounds represented by the general formula (I), Ar ¹ is preferably a phenyl group, a p-tolyl group or a p-anisyl group, which is excellent from the viewpoints of electrophotographic properties, cost and production. Ar ² is a phenylene group or a naphthylene group, Ar ³ is a phenyl group, m
-A tolyl group or a naphthyl group.

Next, specific examples of the sulfur-containing amine compound of the present invention represented by the general formula (I) include those having the structures shown in Tables 1 to 3 below. These do not limit the sulfur-containing amine compound according to the present invention.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

The sulfur-containing amine compound according to the present invention is a novel compound, has a wide conjugated system as shown in the above general formula (I), has high mobility due to electron donation of a sulfur atom, and has a high electrophotographic sensitivity. The residual potential characteristics of the body can be improved. Further, since the sulfur-containing amine compound of the present invention has excellent compatibility with the binder resin, it can be contained in a large amount in the photosensitive layer 4 or 14 to improve the photosensitivity of the electrophotographic photosensitive member.

The electrophotographic photoreceptor according to the embodiment of the present invention can be obtained by containing one or more of the above-mentioned sulfur-containing amine compounds. In some cases, other charge transfer materials 3 may include the following styryl compounds, hydrazone compounds, and triphenylamine compounds.

As styryl compounds, for example, β-phenyl- [4- (benzylamino)] stilbene, β-phenyl
And phenyl- [4- (N-ethyl-N-phenylamino)] stilbene and 1,1-bis (4-diethylaminophenyl) -4,4-diphenylbutadiene.

As the hydrazone compound, for example, 4
-(Dibenzylamino) benzaldehyde-N, N-diphenylhydrazone, 4- (ethylphenylamino) benzaldehyde-N, N-diphenylhydrazone, 4-
Di (p-tolylamino) benzaldehyde-N, N-diphenylhydrazone and 3,3-bis- (4′-diethylaminophenyl) -acrolein-N, N-diphenylhydrazone.

Examples of the triphenylamine compound include, for example, 4-methoxy-4 '-(4-methoxystyryl)
Triphenylamine, 4-methoxy-4'-styryltriphenylamine, triphenylamine dimer (TPD) derivatives and the like.

Various methods are conceivable for obtaining an electrophotographic photosensitive member using these other charge transfer materials 3 and the aforementioned sulfur-containing amine compounds. For example, the above-mentioned sulfur-containing amine compound is added to a sensitizing dye and, if necessary, a chemical sensitizer or an electron-withdrawing compound, and dissolved or dispersed in a binder resin. There is a method of obtaining a single-layer type photoconductor as shown in FIG.

As shown in FIGS. 1 and 2, there is a method of obtaining a photoconductor having a laminated structure including a charge generation layer 5 and a charge transfer layer 6 having high charge generation efficiency. In the case of the photoreceptor shown in FIG. 1, the photosensitive material is provided on the conductive support 1 on the charge generating layer 5 in which a sensitizing dye or a pigment represented by an azo pigment and a phthalocyanine pigment is provided as a main material. The sulfur amine compound is obtained by adding an antioxidant or an electron withdrawing compound as necessary, dissolving or dispersing the compound in the binder resin, and providing this as the charge transfer layer 6. The aforementioned sulfur-containing amine compound can be applied to any of these cases.

The above-mentioned sulfur-containing amine compound is applied onto a conductive support 1 such as a metal drum, a metal plate, a paper which has been subjected to a conductive treatment and a plastic film to form a polymerizable film-forming binder as a binder resin. With the help of the coating, a photoreceptor, in particular a photoreceptor for a copier, is produced.
In this case, in order to further increase the sensitivity, it is desirable to add a substance that imparts plasticity to a polymerizable film-forming binder and a sensitizer, which are binder resins described later, to form a uniform photoconductor film.

As these polymerizable film binders, various ones can be mentioned according to the field of use. In the field of photoconductors for copiers or printers, polystyrene resins, polyvinyl acetal resins, polysulfone resins, polycarbonate resins, polyphenylene oxide resins, polyester resins, alkyd resins, polyarylate resins, and the like are desirable. These may be used alone or in combination of two or more. In particular, resins such as polystyrene, polycarbonate, polyarylate, and polyphenylene oxide have a volume resistance of 10 ¹³ Ω or more, and are excellent in film properties and potential characteristics.

The amount of the polymerizable film binder is 0.1% by weight based on the above-mentioned sulfur-containing amine compound.
It is preferably added in a ratio of 2 to 20 times, more preferably in a range of 0.5 to 5 times. If it is less than 0.2, the sulfur-containing amine compound will precipitate from the surface of the photoreceptor, and if it exceeds 20 times, the sensitivity will be significantly reduced.

In order to use the above-mentioned sulfur-containing amine compound in a printing plate, an alkaline binder is particularly required as a binder resin. The alkaline binder is a polymer substance having an acidic group that is soluble in water or an alcoholic alkaline solvent (including a mixed system). Such acid groups include, for example, acid anhydride groups, carboxyl groups,
A phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, or a sulfonimide group. These alkaline binders preferably have a high acid value of 100 or more. An alkaline binder having a large acid value easily dissolves in an alkaline solvent or easily swells.

Examples of such an alkaline binder include styrene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, vinyl acetate-crotonic acid copolymer, and methacrylic acid-methacrylic acid ester copolymer. Coalescent, phenolic resin, methacrylic acid-styrene-methacrylic acid ester copolymer and the like. The ratio of adding these resins to the above-mentioned sulfur-containing amino compound which is a photoconductive organic substance may be the same as in the case of the above-mentioned photoconductor for a copying machine.

The sensitizing dye added to the photosensitive layer 4 includes triphenylmethane dyes represented by methyl violet, crystal violet, night blue and Victoria blue, erythrosine, rhodamine B, rhodamine 3R, Acridine dyes typified by acridine orange and frappeosin, thiazine dyes typified by methylene blue and methylene green, oxazine dyes typified by capri blue and Meldola blue, other cyanine dyes, styryl dyes, pyrylium salt dyes and thiopyrylium And salt dyes.

Examples of photoconductive pigments that generate charges with extremely high efficiency by light absorption in the photosensitive layer 4 include phthalocyanine pigments such as various metal phthalocyanines, metal-free phthalocyanines and halogen-free metal phthalocyanines, perylene imides and the like. Examples include perylene acid pigments such as perylene anhydride, azo pigments such as bisazo pigments and trisazo pigments, quinacridone pigments and anthraquinone pigments. In particular, as a pigment that generates electric charge, a metal-free phthalocyanine pigment,
An electrophotographic photoreceptor using a titanyl phthalocyanine pigment, a bisazo pigment containing a fluorene ring and a fluorenone ring, a bisazo pigment composed of an aromatic amine, or a trisazo pigment exhibits high sensitivity.

The dye described above may be used as the charge generating substance 2. These dyes may be used alone, but pigments are often used in combination to generate charges with higher efficiency.

In addition to the above-mentioned spectral sensitizers, various chemical substances may be added as necessary for the purpose of preventing an increase in the residual potential, a decrease in the charged potential and a decrease in the sensitivity upon repeated use. I do. As the substance to be added, 1-chloroanthraquinone, benzoquinone, 2,3-dichloronaphthoquinone, naphthoquinone, 4,4′-dinitrobenzophenone, 4,4-dichlorobenzophenone, 4-nitrobenzophenone, 4-nitrobenzalmalone dinitrile Ethyl, α-cyano-β- (p-cyanophenyl) acrylate, 9-anthracenylmethylmalondinitrile, 1-cyano-1- (p-nitrophenyl) -2-
Electron-absorbing compounds such as (p-chlorophenyl) ethylene and 2,7-dinitrofluorenone.
In addition, an antioxidant, an anti-curl agent, a leveling agent, and the like can be added as necessary to the photoreceptor.

The electrophotographic photoreceptor according to the present invention is prepared by dissolving or dispersing the sulfur-containing amine compound in an appropriate solvent together with the above-mentioned additive depending on the form of the photoreceptor to prepare a coating solution. On the conductive support 1 described above and drying. As a solvent for preparing the coating solution, benzene, toluene, aromatic hydrocarbons such as xylene and monochlorobenzene,
Examples include halogenated hydrocarbons such as dichloromethane and dichloroethane, tetrahydrofuran, dioxane, dimethoxymethyl ether and dimethylformamide. These solvents can be used alone or as a mixed solvent of two or more kinds, or if necessary, further added with a solvent such as alcohols, acetonitrile and methyl ethyl ketone.

In FIG. 5, the intermediate layer 8 provided between the conductive support 1 and the photosensitive layer 4
The purpose of the present invention is to provide a protective function and an adhesive function to enhance the coatability of the photosensitive layer 4 and to improve the charge injection from the conductive support 1 to the photosensitive layer. Suitable materials for such an intermediate layer 8 include casein, polyvinyl butyral, polyvinyl alcohol, nitrocellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane, and aluminum oxide gelatin. In addition, polyamide
Nylon 6, nylon 66, nylon 610, copolymerized nylon and alkoxymethylated nylon.

Hereinafter, the sulfur-containing amino compound and the electrophotographic photoreceptor according to the present invention will be described more specifically based on Production Examples, Examples and Comparative Examples. The present invention is not limited by these Production Examples, Examples and Comparative Examples.

First, a production example of a sulfur-containing amine compound used as a charge transfer material in the electrophotographic photosensitive member according to the present invention will be described. In Production Examples 1 and 2, the exemplified compound No. shown in Table 1 was used. 2 and No. It is a manufacture example of the sulfur-containing amine compound of No. 20.

Production Example 1 Under an argon atmosphere, 5.36 g (1.05 equivalent) of ethynylbenzene and 0.082 g (0.01 equivalent) of azobisisobutyronitrile were dissolved in 30 ml of toluene, and p-amino was dissolved therein. A solution prepared by dissolving 6.25 g (1.0 equivalent) of thiophenol in 30 ml of toluene was added with stirring to 10 ml.
Drop in about a minute. After heating under stirring and reacting at 60 ° C. for 2 hours, the solvent was distilled off under reduced pressure and recrystallized from a mixed solvent of toluene / hexane to obtain an intermediate A (yield: 90).
%).

Next, 4.54 g (1.0 equivalent) of intermediate A, 9.16 g (2.1 equivalent) of p-iodotoluene, and 1.06 g (0.5 equivalent) of 18-crown-6-ether were used.
2 equivalents), 5.1 g (4.0 equivalents) of copper powder, and 22.1 g (8.0 equivalents) of anhydrous potassium carbonate were mixed with 150 ml of o-dichlorobenzene, and the mixture was vigorously refluxed with heating and stirring for 30 hours. After completion of the reaction, the filtrate was concentrated by performing hot celite filtration, and the residue was purified by silica gel column chromatography by eluting n-hexane / methylene chloride = 3/7 with methylene chloride only to obtain the desired sulfur-containing compound. 6.3 g of an amine compound (exemplified compound No. 2) was obtained as a white powder compound (yield: 75%). The obtained Exemplary Compound No. ¹ H-NM of second sulfur-containing amine compound
R spectrum (solvent: d-chloroform) was 2.31.
ppm (s, 6H, Me), 6.2-6.7 ppm
(M, 2H, CH = CH) and 6.9-7.3 ppm
(M, 17H, Benzene).

Production Example 2 Under argon atmosphere, 7.32 g (1.05 equivalent) of m-tolylacetylene and 0.099 g (0.01 equivalent) of azobisisobutyronitrile were dissolved in 30 ml of toluene.
14.16 g of p-iodothiophenol (1.
(0 eq.) In 30 ml of toluene is added dropwise over about 10 minutes with stirring. After heating under stirring and reaction at 60 ° C. for 3 hours, the solvent was distilled off under reduced pressure, and recrystallization was performed from a mixed solvent of toluene / hexane to obtain Intermediate B (yield: 84%).

Next, 14.79 g (2.1 equivalent) of intermediate B, 2.14 g (1.0 equivalent) of p-methylaniline, and 1.06 g of 18-crown-6-ether (0.
2 equivalents), 5.1 g (4.0 equivalents) of copper powder, and 22.1 g (8.0 equivalents) of anhydrous potassium carbonate were mixed with 150 ml of o-dichlorobenzene, and the mixture was refluxed vigorously under heating and stirring for 30 hours. After the completion of the reaction, the filtrate was concentrated by performing hot celite filtration, and the residue was purified by silica gel column chromatography.
Purification was performed by eluting only n-hexane / methylene chloride = 3/7 with methylene chloride to obtain 7.6 g of the objective sulfur-containing amine compound (exemplified compound No. 2) as a white powder compound (yield: 66). %). The obtained Exemplified Compound No. The ¹ H-NMR spectrum (solvent: d-chloroform) of the sulfur-containing amine compound ^No. 20 was 2.99 ppm.
(S, 6H, Me), 2.33 ppm (s, 6H, M)
e), 6.2-6.7 ppm (m, 4H, CH = CH)
And 6.9-7.3 ppm (m, 20H, Benze
ne).

In the same manner as in Production Examples 1 and 2, Exemplified Compound No. 3 and No. 3 Thus, a sulfur-containing amine compound No. 8 was obtained.

Examples 1 to 4 and Comparative Example Charge transfer material 3 contained in charge transfer layer 6 shown in FIG.
As the exemplified compound No. obtained as described above.
2, No. 3, No. 8 and No. 20; and 4- (diethylamino) -benzaldehyde-N, N which is a conventionally known charge transfer material.
-Using diphenylhydrazone to form a photosensitive layer 4 having a laminated structure containing each compound,
Four types of electrophotographic photoreceptors of Comparative Example 4 and Comparative Example were produced.

An 80 μm-thick aluminum-evaporated polyester film was used as the conductive support 1, and a bisazo pigment represented by the following structural formula (VI) was coated thereon with a phenoxy resin (P
KHH: Union Carbide (manufactured by Union Carbide) is added to a 1% tetrahydrofuran (THF) solution in the same amount as the resin in a weight ratio. The dispersion was carried out for a time, applied and dried by a doctor blade method. The film thickness after drying was 0.2 μm.

[0084]

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On this pigment layer (charge generation layer), Exemplified Compound No. 2, No. 3, No. 8 or No. 20 and 1 g of polyarylate resin (U-100: manufactured by Unitika)
A solution of 1.2 g in tetrahydrofuran (15
%) Was applied by a squeezing doctor to form a resin-sulfur-containing amine compound solid solution phase (charge transfer layer) having a dry film thickness of 25 μm, thereby producing electrophotographic photoreceptors of Examples 1 to 4. In addition, as a comparative example, an electron-emitting device was prepared in the same manner as in the example except that 4- (diethylamino) -benzaldehyde-N, N-diphenylhydrazone, which is a conventionally known charge transfer material, was used instead of the exemplified compound. A photoreceptor was prepared.

The electrophotographic characteristics of the laminated electrophotographic photosensitive member prepared as described above were measured using an electrostatic recording paper test apparatus (SP-
428: manufactured by Kawaguchi Electric). The measurement conditions are
Applied voltage: -6 kV, Static: No. The exposure amount E100 (lux seconds) and the initial potential V0 (-volt) required to attenuate from -700 V to -100 V by white light irradiation (irradiation light: 5 lux) were measured. The values are shown in Table 4 as the first values. Further, using the same apparatus, the same operation was performed 10,000 times with one cycle of charge-discharge (discharge light: irradiation of white light of 40 lux for 1 second), and then a second exposure E100 (lux · sec) ) And the initial potential V0 (-volt) are measured, and E100 and V
The change of 0 was examined.

[0087]

[Table 4]

From Table 4, it was found that the photoreceptor using the sulfur-containing amine compound according to the present invention had better sensitivity and repetition characteristics than the conventional compound.

Example 5 Charge transfer material 3 contained in charge transfer layer 6 shown in FIG.
As the exemplified compound No. obtained as described above. 2
The photosensitive layer 4 having a laminated structure containing the sulfur-containing amine compound shown in (1) was formed, whereby an electrophotographic photosensitive member of Example 5 was produced.

On an aluminum evaporated polyester film,
0.4 g of an X-type metal-free phthalocyanine (Fastgen Blue 8120: manufactured by Dainippon Ink) represented by the following structural formula (VII) is added to a vinyl chloride-vinyl acetate copolymer resin (ESLEX M: manufactured by Sekisui Chemical Co., Ltd.) 0 0.3 g was dissolved in 30 ml of an ethyl acetate solution, dispersed in a paint conditioner for about 20 minutes, applied by a doctor blade method, and formed a charge generation layer so that the film thickness after drying was 0.4 μm. I let it.

[0091]

Embedded image

On the formed charge generation layer, the compound of the exemplary compound No. A photoreceptor comprising two layers was prepared by laminating polyarylate layers containing the sulfur-containing amine compound No. 2 at a weight ratio of 50%.

The energy (E50) required for halving the potential and the initial potential (-V0) of the produced photoreceptor were measured using light of 780 nm, and V0 = -700 (volts) and E50 = 0.21 ( μJ / cm ² ) and a highly charged photoreceptor.

A laser printer (WD-580P:
Was modified, and the photoreceptor was stuck to the drum portion. After performing continuous blank copy (Non Copy Aging) 10,000 times, the initial potential drop and the sensitivity drop were also examined.
As a result, V0 = -685 (volt), E50 = 0.22
(ΜJ / cm ² ) and little change in the value compared to the first time.

Examples 6 to 9 As the charge transfer material 3 shown in FIG.
4, No. 7, No. 10 and no. A single photosensitive layer 4 containing each of the sulfur-containing amine compounds shown in No. 15 was formed, and four types of electrophotographic photosensitive members of Examples 6 to 9 were produced.

The exemplified compound no. 4, No. 7, No. 1
0 or No. 15 as 1 g, a polycarbonate resin represented by the following structural formula (VIII) 1.1 g, N, N-3,
0.15 g of 5-xylyl-3,4,9,10-perylenetetracarboximide and 0.05 UV absorber
g was dissolved in methylene chloride to prepare a solution. In the prepared solution, the imide compound is partially dispersed. The solution was applied by an applicator onto a support having a 7 μm alumite layer on the surface of an aluminum substrate and subjected to alumite processing to obtain a single-layer photoreceptor having a dry film thickness of 20 μm.

[0097]

Embedded image

The electrophotographic characteristics of the photoreceptor produced as described above were evaluated using an electrostatic recording paper test apparatus. The measurement conditions were as follows: applied voltage: 5.5 kV, static: No. 3
And Exposure amount E100 (looks-second) required to attenuate from +700 V to +100 V by white light irradiation
Was measured, and the values are shown in Table 5. The empty copy test was performed 10,000 times, and the degree of decrease in sensitivity (E100) is also shown in Table 5.

[0099]

[Table 5]

From Table 5, it was found that the photoreceptor using the sulfur-containing amine compound according to the present invention had excellent sensitivity and repetition characteristics even in positive charging.

[0101]

As described above, according to the present invention, a novel sulfur-containing amine compound represented by the above general formula (I) can be provided.

According to the present invention, there is provided an organic electrophotographic photoreceptor having high sensitivity and high durability by containing the sulfur-containing amine compound represented by the general formula (I) as a charge transfer material. be able to. The electrophotographic photoreceptor is nontoxic, has no problem in resources, has good transparency, is lightweight, has excellent film-forming properties, has both positive and negative charging properties, and is easy to manufacture, as compared with inorganic photoreceptors. In addition to the advantages of the organic photoreceptor described above, the photoreceptor has excellent characteristics that the photosensitivity hardly decreases even when it is used repeatedly.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a layer configuration of an electrophotographic photoreceptor according to the present invention in which a charge transfer layer 6 is formed on a charge generation layer 5 on a conductive support 1.

FIG. 2 is a cross-sectional view schematically showing a layer configuration of an electrophotographic photoreceptor according to the present invention in which a charge generation layer 5 is formed on a charge transfer layer 6 on a conductive support 1.

FIG. 3 is a cross-sectional view schematically showing a layer configuration of an electrophotographic photosensitive member according to the present invention, in which a photosensitive layer 14 containing a charge generating substance 2 and a charge transfer substance 3 is formed on a conductive support 1.

4 is a diagram in which a surface protective layer 7 is provided on the photosensitive layer 14 of FIG.
FIG. 1 is a cross-sectional view schematically illustrating an electrophotographic photosensitive member according to the present invention.

FIG. 5 is a cross-sectional view schematically showing an electrophotographic photosensitive member according to the present invention in which an intermediate layer 8 is provided between the conductive support 1 and the photosensitive layer 4 of FIG.

[Description of Signs] 1 conductive support 2 charge generation material 3 charge transfer material 4, 14 photosensitive layer 5 charge generation layer 6 charge transfer layer 7 surface protection layer 8 intermediate layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H068 AA20 AA21 AA31 AA37 BA13 4C037 QA07 4H006 AA01 AB76 AB91 TA04 TB23 TC21

Claims (8)

[Claims] 1. A sulfur-containing amine compound represented by the following general formula (I). Embedded image (Wherein, Ar ¹ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Ar
² represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Ar ³ is an aryl group that may have a substituent, a heterocyclic group that may have a substituent, an aralkyl group that may have a substituent, and a carbon atom that may have a substituent has 1 to 1 carbon atoms. 5 represents a 5-alkyl group, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent or a perfluoroalkyl group having 1 to 5 carbon atoms which may have a substituent. n is 1 to
Indicates an integer of 3. ) 2. A photosensitive layer provided on a conductive support,
An electrophotographic photoreceptor comprising a sulfur-containing amine compound represented by the following general formula (I). Embedded image (Wherein, Ar ¹ represents an aryl group which may have a substituent or a heterocyclic group which may have a substituent. Ar
² represents an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Ar ³ is an aryl group that may have a substituent, a heterocyclic group that may have a substituent, an aralkyl group that may have a substituent, and a carbon atom that may have a substituent has 1 to 1 carbon atoms. 5 represents a 5-alkyl group, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent or a perfluoroalkyl group having 1 to 5 carbon atoms which may have a substituent. n is 1 to
Indicates an integer of 3. ) 3. The electrophotographic photoreceptor according to claim 2, wherein the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (II). Embedded image (Wherein, Ar ⁴ and Ar ⁵ are an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, an aralkyl group optionally having a substituent, A C 1-5 alkyl group, a C 1-5 fluoroalkyl group which may contain a substituent or a C 1-5 perfluoroalkyl group which may contain a substituent Ar ¹ and Ar ² have the general formula (I)
Is the same as that shown in ) 4. The electrophotographic photoconductor according to claim 2, wherein the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (III). Embedded image (In the formula, a has 1 to 3 carbon atoms that may contain a substituent.
Having 1 to 1 carbon atoms which may contain a substituent
5 fluoroalkyl groups, a perfluoroalkyl group having 1 to 5 carbon atoms which may contain a substituent, 1 to 3 carbon atoms
An alkoxy group, a C1 to C3 dialkylamino group,
It represents a halogen atom or a hydrogen atom, and m represents an integer of 1 to 4. However, when m is 2 or more, each a may be the same or different, and may form a ring with each other. Ar ¹ , Ar ⁴
And Ar ⁵ have the same meanings as those represented by formula (II). ) 5. The electrophotographic photoreceptor according to claim 2, wherein the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (IV). Embedded image (Wherein b, c and d are each an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, a substituent A perfluoroalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom, which may contain
l, k and j each represent an integer of 1 to 4. Where l,
When k and j are each 2 or more, the corresponding b,
c and d may be the same or different, and may form a ring with each other. a and m have the same meanings as those represented by formula (III). ) 6. The electrophotographic photosensitive member according to claim 2, wherein the sulfur-containing amine compound represented by the general formula (I) is a compound represented by the following general formula (V). Embedded image (Wherein, e and f each include an alkyl group having 1 to 3 carbon atoms which may have a substituent, a fluoroalkyl group having 1 to 5 carbon atoms which may have a substituent, and a substituent Represents a perfluoroalkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group having 1 to 3 carbon atoms, a halogen atom or a hydrogen atom; When i and h are 2 or more, corresponding e and f may be the same or different and may form a ring with each other, and a, b, m and l are represented by the general formula (IV) Is synonymous with that shown in.) 7. The photosensitive layer has a laminated structure of a charge generation layer containing a charge generation material and a charge transfer layer containing a charge transfer material containing the sulfur-containing amine compound. 2. The electrophotographic photosensitive member according to 2. 8. The electrophotographic photoreceptor according to claim 2, wherein said photosensitive layer comprises a single layer containing a charge generating substance and a charge transfer substance containing said sulfur-containing amine compound.