JPH06222598A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To provide an electrophotographic sensitive body excellent in photosensitive characteristics, having a high strength to thermal and mechanical shocks and capable of being produced at a low cost. CONSTITUTION:A photosensitive layer contg. at least one kind of olefin compd. having a pyrenyl group represented by the formula as an effective component is formed on an electric conductive substrate. In the formula, each of R1 and R2 is H, a halogen, nitro, cyano, optionally substd. alkyl, etc., each of R3 and R4 is H, cyano, alkoxycarbonyl, optionally substd. alkyl, etc., R5 is H, a lower alkyl or alkoxy, W is H, an optionally substd. alkyl, etc., (j) is an integer of 1-5, (k) is an integer of 1-4, (l) is an integer of 0-2, (m) is 1 or 2 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 photoreceptor, and more particularly to an electrophotographic photoreceptor having a photosensitive layer containing a specific compound.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide and zinc oxide have been used as photoconductive materials for photoconductors used in electrophotography.
The term "electrophotographic method" generally means that a photoconductive photoconductor is first charged in a dark place by, for example, corona discharge, and then imagewise exposed to selectively dissipate the charge only in the exposed portion. An electrostatic latent image is obtained, and this latent image portion is developed with electroscopic fine particles (toner) composed of a coloring material such as a dye or pigment and a binder such as a polymer substance to be visualized to form an image. This is one of the image forming methods.

The basic characteristics required for a photoconductor in such an electrophotographic method are: (1) being able to be charged to an appropriate potential in a dark place, (2) being small in dissipation of a charge in a dark place, (3) It is possible to rapidly dissipate the charge by light irradiation.

By the way, in reality, each of the above-mentioned inorganic substances has various advantages and, at the same time, has various drawbacks. For example, selenium, which is widely used at present, sufficiently satisfies the above conditions (1) to (3), but the manufacturing conditions are difficult, the manufacturing cost is high, the selenium is not flexible, and it is processed into a belt shape. It is difficult to handle, and it is sensitive to heat and mechanical shocks, so it requires careful handling. Cadmium sulfide and zinc oxide are used as photoconductors by dispersing them in a resin as a binder, but since they have mechanical defects such as smoothness, hardness, tensile strength and abrasion resistance, they can be repeated as they are. Can not be used.

In recent years, electrophotographic photoconductors using various organic substances have been proposed and some have been put to practical use in order to eliminate the drawbacks of these inorganic substances. For example, a photoreceptor comprising poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (U.S. Pat. No. 34,34).
84237), a photoconductor obtained by sensitizing poly-N-vinylcarbazole with a pyrylium salt dye (described in JP-B-48-25658), and a photoconductor containing an organic pigment as a main component (special JP-A-47-37543), a photoreceptor containing a eutectic complex composed of a dye and a resin as a main component (described in JP-A-47-10735), and a triphenylamine compound dye-sensitized. (US Pat. No. 3,180,730), a photoreceptor using an amine derivative as a charge transport material (JP-A-57-195254), poly-N-vinylcarbazole and an amine derivative as a charge transport material. Photoreceptor used (JP-A-58-11)
55), a photoconductor using a benzidine compound among polyfunctional tertiary amine compounds as a photoconductive material (U.S. Pat. No. 3,265,496, JP-B-39-11546, JP-A-53-27033). ) And so on. These photoconductors have excellent properties and are considered to be of high value practically.However, in consideration of various demands on the photoconductor in the electrophotographic method, these demands are still insufficient. It is the actual situation that nothing satisfying the above is obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the various drawbacks of the above-described conventional photoconductor and to provide a photoconductor which can sufficiently satisfy the conditions required in the electrophotographic method. Especially. Another object of the present invention is to provide an electrophotographic photosensitive member which is easy to manufacture, relatively inexpensive, and excellent in durability.

[0007]

According to the present invention, at least one olefin compound having a pyrenyl group represented by the following general formula (I) (Formula 1) is contained as an active ingredient on a conductive support. Provided is an electrophotographic photoreceptor having a photosensitive layer.

[Chemical 1] (In the above formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and are the same. Or they may be different R
₃ , R ₄ represent a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different. R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group. W is a hydrogen atom, a substituted or unsubstituted alkyl group, a phenylthio group, a chain unsaturated hydrocarbon group divalent group, a substituted or unsubstituted carbocyclic aromatic group monovalent group or divalent group, substituted or It represents a monovalent group or a divalent group of an unsubstituted heterocyclic group. j is 1 to 5, k is 1 to 4, l
Is an integer of 0 to 2, m is 1 or 2, and n is an integer of 1 to 3. When j, k, or n is 2 or more, R ₁ , R ₂ , R
₅ may be the same or different. )

In the present invention, the olefin compound having a pyrenyl group represented by the general formula (I) (formula 1) contained in the photosensitive layer is, for example, the general formula (II) (formula 2).

[Chemical 2] (In the above formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and are the same. Or they may be different R
₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group. j is an integer of 1 to 5, k is an integer of 1 to 4, and n is an integer of 1 to 3. When j or k and n are 2 or more, R ₁ , R ₂ and R ₅
May be the same or different. ) And an aldehyde compound represented by the following general formula (III)

[Chemical 3] (In the above formula, R ₃ and R ₄ represent a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and they may be the same or different. _{P + (R 6) 3 Y} - (. wherein R ₆ represents a phenyl group or a lower alkyl group, Y represents a halogen atom) phosphonium salt or -PO represented by (oR _{7) 2} (wherein R ₇ Represents a lower alkyl group), and W represents a hydrogen atom, a substituted or unsubstituted alkyl group, a phenylthio group, a divalent group of a chain unsaturated hydrocarbon group, a substituted or unsubstituted group. Represents a monovalent or divalent group of a carbocyclic aromatic group, a monovalent group or a divalent group of a substituted or unsubstituted heterocyclic group, l is an integer of 0 to 2, and m is 1 or 2. Representation) With a phosphorus compound of formula (IV)

[Chemical 4] (In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , W and j, k, l, m
Is the same as the definition of claim 1. ) With a secondary amine compound represented by the following general formula (V)

[Chemical 5] (In the above formula, R ₅ and n are the same as defined in claim 1.
Z represents a halogen atom. ) And a pyrene compound represented by the formula (1).

The olefin compound having a pyrenyl group of the general formula (I) (Formula 1) obtained by the above-mentioned production method will be described in more detail. In the general formula (I) (formula 1), R _{1 to} R ₅
The following can be mentioned as specific examples of W and W, or as their substituents.

(1) Halogen atom: Fluorine, chlorine, bromine and iodine are mentioned. (2) Alkyl groups, preferably C _{1 to} C _12, especially C ₁
-C _9, more preferably a straight-chain or branched alkyl group of C ₁ -C _4, these alkyl groups may be further substituted fluorine atom, a hydroxyl group, a cyano group, an alkoxy group of C ₁ -C _4,
A phenyl group substituted with a phenyl group or a halogen atom, a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkoxy group may be contained. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group,
s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group Group, 4-methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like. (3) Alkoxy group (-OR ₈ ); R ₈ represents the alkyl group defined in (2). Specifically, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, t-butoxy group, n-butoxy group, s-butoxy group, i-butoxy group, 2-hydroxyethoxy group, 2-cyano. Examples thereof include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group and a trifluoromethoxy group. (4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4
-Methylphenoxy group, 4-methoxyphenoxy group, 4
Examples include -chlorophenoxy group and 6-methyl-2-naphthyloxy group. (5) an alkylthio group (-SR _8), phenylthio group of the following

[Chemical 6]R₈Represents an alkyl group defined in (2). Specifically
Is methylthio group, ethylthio group, phenylthio group, p-
Examples thereof include a methylphenylthio group. Represents an alkyl group or an aryl group represented by
Are, for example, phenyl group, biphenylyl group or naphthyl group.
Cyl groups, which are C₁~ C_FourAn alkoxy group of
C₁~ C_FourOr the halogen atom as a substituent
May be included. R₉And R_TenEven if they form a ring together
good. It also forms a ring with the carbon atom on the aryl group.
May be. ) Specifically, an amino group, diethylamino
Group, N-methyl-N-phenylamino group, N, N-diph
Phenylamino group, N, N-di (p-tolyl) amino
Group, dibenzylamino group, piperidino group, morpholino
Group, a julolidyl group and the like. (7) such as methylenedioxy group or methylenedithio group
An alkylenedioxy group or an alkylenedithio group,Represents a radical. Specifically, methoxycarbonyl group, ethoxycarbonyl group
And the like. (9) Cyano group (-CN) (10) Nitro group (-NO₂) (11) The following phenyl groups

[Chemical 7] R ₁₁ represents a hydrogen atom or a substituent defined in (1) to (10). For example, phenyl group, tolyl group, methoxyphenyl group, benzylphenyl group, chlorophenyl group,
Examples include 3,4-methylenedioxyphenyl group and the like.

When W is a divalent chain unsaturated hydrocarbon group, for example, a vinylene group (-CH = CH-), 1,3-
Butadienylene group (-CH = CH-CH = CH-) and the like, and in the case of a carbocyclic aromatic group, a phenyl group, a biphenyl group, a terphenyl group and the like can be mentioned as the non-fused carbocyclic aromatic group, Examples of the condensed polycyclic hydrocarbon group include a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptanenyl group, a biphenylenyl group, and an as- group.
Indacenyl group, fluorenyl group, s-indacenyl group, acenaphthylenyl group, preyadenyl group, acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrylenyl group, aceanthrylenyl group, triphenylenyl group, Examples thereof include a pyrenyl group, a chrysenyl group, and a naphthacenyl group.

When W is a heterocyclic hydrocarbon group, the following can be mentioned. Pyridyl group, pyrimidyl group, pyrazinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, coumarinyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, dibenzofuranyl group, benzothienyl group, dibenzo Thienyl group, indolyl group, carbazolyl group, pyrazolyl group, imidazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, indazolyl group, benzothiazolyl group, pyridazinyl group, cinnolinyl group, quinazolinyl group, quinoxalyl group, phthalazinyl group, phthalazinedionyl group , Chromonyl group, naphtholactonyl group, quinononyl group, o-sulfobenzoic acid imidyl group, maleic acid imidyl group, naphthalidinyl group, benzimidazolonyl group, benzoxazolonyl group, benzothiazolonyl group Group,
Benzothiazothionyl group, quinazolonyl group, quinoxalonyl group, phthalazonyl group, dioxopyrimidinyl group, pyridonyl group, isoquinononyl group, isoquinolyl group, isothiazolyl group, benzisoxazolyl group, benzisothiazolyl group, indazolonyl group, acridinyl group , An acridonyl group, a quinazoline dionyl group, a quinoxaline dionyl group, a benzoxazine dionyl group, a benzoxazinyl group, a naphthalimidyl group, a tetrahydrofuryl group, a tetrahydrothienyl group, a piperazino group, a piperazinyl group and a pyrrolidinyl group.

As mentioned above, divalent groups of these cyclic aromatic groups can also be mentioned, and they may further have the substituents defined in (1) to (11).

[Table-1 (1)]

[Chemical 1]

[Table 1- (2)]

[Table 1- (3)]

[Table 1- (4)]

[Table 1- (5)]

[Table 1- (6)]

[Table 1- (7)]

[Table 1- (8)]

The photoconductor of the present invention comprises a photosensitive layer 2 (2 ', 2 ", 2"' or 2 "") containing one or more olefin compounds having a pyrenyl group as described above. However, it can be used as shown in FIG. 1, FIG. 2, FIG. 3, FIG. 4 or FIG. 5 depending on the application of these olefin compounds having a pyrenyl group.

The photoconductor in FIG. 1 comprises a conductive support 1 provided with a photoconductive layer 2 comprising an olefin compound having a pyrenyl group, a sensitizing dye and a binder (binder resin). The olefin compound having a pyrenyl group here acts as a photoconductive substance, and the generation and transfer of charge carriers required for light attenuation are performed via the olefin compound having a pyrenyl group. However, since the olefin compound having a pyrenyl group has almost no absorption in the visible region of light, for the purpose of forming an image with visible light, a sensitizing dye having absorption in the visible region is added to perform sensitization. There is a need to.

In the photoreceptor shown in FIG. 2, a photosensitive layer 2'in which a charge generating substance 3 is dispersed in a charge carrier medium 4 composed of an olefin compound having a pyrenyl group and a binder is provided on a conductive support 1. It has been done. The olefin compound having a pyrenyl group here forms a charge carrier medium together with a binder (or a binder and a plasticizer), while the charge generating substance 3 (a charge generating substance such as an inorganic or organic pigment) is a charge carrier. To occur. In this case, the charge carrier medium 4
Mainly takes charge of the function of receiving the charge carrier generated by the charge generating substance 3 and carrying it. In this photoreceptor, the basic condition is that the charge-generating substance and the olefin compound having a pyrenyl group do not overlap in the absorption wavelength region, mainly in the visible region. This is because it is necessary to transmit light to the surface of the charge generating substance 3 in order to efficiently generate charge carriers in the charge generating substance 3. The olefin compound having a pyrenyl group represented by the general formula (I) has almost no absorption in the visible region, and when it is combined with the charge generating substance 3 that generally absorbs light in the visible region and generates a charge carrier, it is particularly effective. Its feature is that it works as a charge carrier substance.

The photoconductor in FIG. 3 comprises a charge generating layer 5 mainly composed of a charge generating substance 3 on a conductive support 1, and a charge carrier layer 4 containing an olefin compound having a pyrenyl group.
Is provided with a photosensitive layer 2 ″.
In this photoreceptor, the light transmitted through the charge transport layer 4 reaches the charge generation layer 5 and the charge carriers are generated in that region, while the charge transport layer 4 receives the injection of the charge carriers and carries them. The generation of charge carriers required for light attenuation is performed by the charge generating substance 3, and the charge carriers are transported by the charge transport layer 4 (mainly the olefin compound having a pyrenyl group works). Such a mechanism is the same as that explained for the photoconductor shown in FIG.

The photoreceptor in FIG. 4 has a third charge generation layer 5
And the charge carrier layer 4 containing the olefin compound having a pyrenyl group is laminated in the reverse order, and the mechanism for generating and carrying the charge carrier can be the same as described above. In this case, considering the mechanical strength, the protective layer 6 may be provided on the charge generation layer 5 as shown in FIG.

In order to actually produce the photoreceptor of the present invention, the process shown in FIG.
In the case of the photoreceptor shown in 1), one or more olefin compounds having a pyrenyl group are dissolved in a solution in which a binder is dissolved, and a sensitizing dye is added to the solution to prepare a conductive solution. The photosensitive layer 2 may be formed by coating on the support 1 and drying.

The thickness of the photosensitive layer is 3 to 50 μm, preferably 5 to 20 μm. The amount of the olefin compound having a pyrenyl group in the photosensitive layer 2 is 30 to 70% by weight,
It is preferably about 50% by weight, and the amount of the sensitizing dye in the photosensitive layer 2 is 0.1 to 5% by weight, preferably 0.5.
~ 3% by weight. As sensitizing dyes, triarylmethane dyes such as Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6B, Rhodamine B, Rhodamine 6G, Rhodamine G Extra, Eosin S, Erythrosine, Rose Bengal, Fluorescein are available. Xanthene dyes, methylene blue-like thiazine dyes, cyanine-like cyanine dyes, 2,6-diphenyl-4
-(N, N-dimethylaminophenyl) thiapyrylium perchlorate, benzopyrylium salt (Japanese Patent Publication No. 48-2
Pyrylium dyes such as those described in Japanese Patent No. 5658). In addition, these sensitizing charges may be used alone or in combination of two or more kinds.

To prepare the photoreceptor shown in FIG. 2, fine particles of the charge generating substance 3 are dispersed in a solution in which an olefin compound having one or more pyrenyl groups and a binder are dissolved. This may be applied on the conductive support 1 and dried to form the photosensitive layer 2 '.

The thickness of the photosensitive layer 2'is 3 to 50 μm, preferably 5 to 20 μm. The amount of the olefin compound having a pyrenyl group in the photosensitive layer 2'is 10 to 95% by weight, preferably 30 to 90% by weight, and the amount of the charge generating substance 3 in the photosensitive layer 2'is 0.1 to 10. It is 50% by weight, preferably 1 to 20% by weight. Charge generation material 3
Examples of the inorganic pigments include selenium, selenium-tellurium, cadmium sulfide, cadmium sulfide-selenium, and α-silicon. Organic pigments include, for example, CI Pigment Blue 25 (color index CI 21180) and CI Pigment Red 41 (CI 21200). , CI Acid Red 52 (CI 45100), CI Basic Red 3 (CI 45210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033), and an azo pigment having a distyrylbenzene skeleton (JP-A-53). -133445), an azo pigment having a triphenylamine skeleton (Japanese Patent Application Laid-Open No. 53-13234).
7), an azo pigment having a dibenzothiophene skeleton (described in JP-A-54-21728), an azo pigment having an oxadiazole skeleton (JP-A-54-12).
742), azo pigments having a fluorenone skeleton (described in JP-A-54-22834), azo pigments having a bisstilbene skeleton (JP-A-54-1773).
3), an azo pigment having a distyryl oxadiazole skeleton (described in JP-A-54-2129), an azo pigment having a distyryl carbazole skeleton (described in JP-A-54-14967). Azo pigments such as CI Pigment Blue 16 (CI 74
100) and other phthalocyanine pigments, for example, CIVAT BROWN 5 (CI 73410), CIVAT Die (CI 73030) and other indigo pigments, Argos Scarlet B (manufactured by Bayer), Indanthren Scarlet R (manufactured by Bayer). And the like, such as perylene pigments. These charge-generating substances may be used alone or in combination of two or more.

Further, in order to manufacture the photoconductor shown in FIG. 3, a charge generating substance is vacuum-deposited on the conductive support 1 or more, or fine particles 3 of the charge generating substance are dissolved in a binder, if necessary. The charge generation layer 5 is prepared by applying a dispersion liquid dispersed in a different solvent and drying it, and further, if necessary, surface finishing and film thickness adjustment by a method such as buffing.
Then, a solution in which an olefin compound having one or more types of pyrenyl groups and a binder are dissolved is applied thereon and dried to form the charge transport layer 4. The charge generating material used for forming the charge generating layer 5 is the same as that described in the description of the photosensitive layer 2 '.

The charge generation layer 5 has a thickness of 5 μm or less, preferably 2 μm or less, and the charge transport layer 4 has a thickness of 3 to 50.
μm, preferably 5 to 20 μm is suitable. When the charge generation layer 5 is of a type in which the fine particles 3 of the charge generation layer substance are dispersed in a binder, the proportion of the fine particles 3 of the charge generation substance in the charge generation layer 5 is 10 to 95% by weight, preferably Is about 50 to 90% by weight. In addition, the charge transport layer 4
The amount of the compound in 10 to 95% by weight, preferably 3
It is 0 to 90% by weight. To prepare the photoreceptor shown in FIG. 4, a solution in which an olefin compound having a pyrenyl group and a binder is dissolved is applied on the conductive support 1 and dried to form the charge transport layer 4, The charge generation layer 5 may be formed by coating fine particles of the charge generation layer substance on the charge transfer layer, and optionally by dispersing a dispersion liquid in a solvent in which a binder is dissolved by a method such as spray coating. . The amount ratio of the charge generation layer or the charge transport layer is the same as that described in FIG. The charge generation layer 5 of the photoconductor thus obtained
By further forming an appropriate resin solution on the protective layer 6 by a method such as spray coating, the photoreceptor shown in FIG. 5 can be prepared. As the resin used here, the binder described below can be used.

In the production of any of these photoreceptors, a metal plate or metal foil such as aluminum, a plastic film deposited with a metal such as aluminum, or a paper subjected to a conductive treatment is used as the conductive support 1. To be Further, as the binder, condensation resins such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide are used. All insulating and adhesive resins can be used. If necessary, a plasticizer is added to the binder, and examples of such a plasticizer include halogenated paraffin, polychlorinated biphenyl, dimethylnaphthalene, dibutyl phthalate and the like.

Further, the photoreceptor obtained as described above may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary. Materials used for these layers include polyamide, nitrocellulose,
Aluminum oxide or the like is preferable, and the film thickness is preferably 1 μm or less. To make a copy using the photoreceptor of the present invention,
After the photosensitive surface is charged and exposed, it is developed and, if necessary, transferred to paper or the like. The photoconductor of the present invention has excellent advantages such as high sensitivity and high flexibility.

[0027]

EXAMPLES The present invention will be described below with reference to examples. In the following examples, all parts are parts by weight.

[Specific Example of Compound No. Synthesis Example of (1)] N
2.47 g (6.0 mmol) of-(4-formylphenyl) -N- (4-methylphenyl) -1-aminopyrene
And diethyl benzylphosphonate 1.64g (7.2mm
ol) was added to 30 ml of N, N-dimethylformamide, to which 1.39 g of 25% sodium methylate was added.
(7.2 mmol) was added dropwise at room temperature over 10 minutes. After stirring at room temperature for 3 hours, the mixture was poured into 200 ml of ice water, acetic acid was added to neutralize, and the mixture was stirred for 30 minutes. The formed precipitate was collected by filtration, washed with water, further washed with methanol, and dried to obtain 2.78 g of a crude product (yield 95.2%). This was treated with a silica gel column (eluent: toluene / n-hexane: 1 /
3 vol. ), And recrystallized with a mixed solvent of ethanol / ethyl acetate to give yellow needle crystals of N- (4-methylphenyl) -N- (4-styrylphenyl) -1-aminopyrene (1.87 g, yield 64. 0%). Melting point is 14
It was 2.8 ° C (TG-DTA endothermic peak temperature). The elemental analysis values were as follows as C ₃₇ H ₂₇ N.

Example 1 As a charge generating substance, 76 parts of Diane Blue (CI Pigment Blue 25, CI21180), 1260 parts of a 2% tetrahydrofuran solution of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) and 3700 parts of tetrahydrofuran were placed in a ball mill. The obtained dispersion liquid was pulverized and mixed with a doctor blade to form a charge generating layer having a thickness of about 1 μm on the aluminum surface of a conductive aluminum-deposited polyester base, which was then dried. . On the other hand, as the charge carrier substance, compound specific example No. Olefin compound 2 having 1 pyrenyl group
Section, polycarbonate resin (Panlite K1300,
2 parts of Teijin Co., Ltd. and 16 parts of tetrahydrofuran were mixed and dissolved to form a solution, which was then applied onto the charge generation layer using a doctor blade, and then at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes. After being dried, a charge carrying layer having a thickness of about 20 μm was formed, and the photoconductor No. Created 1.

Examples 2 to 81 In the same manner as in Example 1 except that the charge generating substance and the charge carrier substance (olefin compound having a pyrenyl group) were replaced by those shown in Table 2, the photoreceptor No. 2 to 81 were created.

[Table 2- (1)]

[Table 2- (2)]

[Table 2- (3)]

[Table 2- (4)]

[Table 2- (5)]

[Table 2- (6)]

[Table 2- (7)]

[Table 2- (8)]

[Table 2- (9)]

Example 82 Selenium was vacuum-deposited to a thickness of about 1 μm on an aluminum plate having a thickness of about 300 μm to form a charge generation layer. Then No. Olefin compound 2 having 1 pyrenyl group
Part, polyester resin (DuPont Polyester Adhesive 49000) 3 parts and tetrahydrofuran 4
5 parts were mixed and dissolved to form a charge transport layer forming liquid, which was applied onto the above charge generation layer (selenium vapor deposition layer) using a doctor blade, air-dried, and then dried under reduced pressure to a thickness. With the charge carrier layer having a thickness of about 10 μm formed, the photosensitive member No. I got 82.

Example 83 Perylene pigment instead of selenium

[Chemical 8] To form a charge generation layer (thickness is about 0.6 μm) and has a pyrenyl group as a charge carrier substance. In the same manner as in Example 82 except that the photoconductor No. 1 was used. 83 was created.

Example 84 A mixture of 1 part of Diane Blue (the same as that used in Example 1) and 158 parts of tetrahydrofuran was pulverized and mixed in a ball mill, and then No. 12 parts of olefin compound having 1 pyrenyl group, polyester resin (DuPont polyester adhesive 49000)
18 parts was added and the mixture was further mixed to obtain a photosensitive layer forming liquid,
It was applied onto an aluminum vapor-deposited polyester film using a doctor blade and dried at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of about 16 μm. 84 was created.

Example 85 On a polyester film substrate vapor-deposited on aluminum,
The charge transport layer coating liquid used in Example 1 was blade coated in the same manner as in Example 1, and then dried to form a charge transport layer having a thickness of about 20 μm. Bisazo pigment (P-2) 13.
5 parts, polyvinyl butyral (trade name: XYHL Union Carbide Plastic Co., Ltd.) 5.4 parts, THF 6
After 80 parts and 1020 parts of ethyl cellosolve were pulverized and mixed in a ball mill, 1700 parts of ethyl cellosolve were added and mixed by stirring to obtain a charge generation layer coating liquid. This coating solution is spray-coated on the above charge transport layer, and the coating is carried out at 100 ° C. for 1 hour.
It was dried for 0 minutes to form a charge generation layer having a thickness of about 0.2 μm. Further, a methanol / n-butanol solution of a polyamide resin (trade name: CM-8000, manufactured by Toray) is spray-coated on the charge generation layer and dried at 120 ° C. for 30 minutes to form a protective layer having a thickness of about 0.5 μm. To form photoconductor N
o. 85 was created.

Photoreceptor No. 1 thus prepared 1-85
For the above, using a commercially available electrostatic copying paper tester (type SP428 manufactured by KK Kawaguchi Denki Seisakusho), a corona discharge of -6KV or + 6KV was performed for 20 seconds to charge the sample, and then the sheet was left in a dark place for 20 seconds, and the surface at that time was measured. The potential Vpo (volt) is measured, and then the tungsten lamp light is irradiated so that the illuminance on the surface of the photoconductor becomes 4.5 lux, and the time (second) until the surface potential becomes 1/2 of Vpo is obtained. , Exposure amount E
½ (lux · sec) was calculated. The results are shown in Table 3.

After charging each of the above photoconductors by using a commercially available electrophotographic copying machine, light irradiation is performed through the original image to form an electrostatic latent image, which is developed with a dry developer. When the obtained image (toner image) was electrostatically transferred onto plain paper and fixed, a clear transferred image was obtained. Even when a wet type developer was used as the developer, a clear transfer image was similarly obtained.

[Table 3- (1)]

[Table 3- (2)]

[Table 3- (3)]

[Table 3- (4)]

[Table 3- (5)]

[Table 3- (6)]

[Table 3- (5)]

[0037]

The photoconductor of the present invention is not only excellent in photosensitivity, but also has a high strength against heat and mechanical shocks and can be manufactured at low cost.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view of an electrophotographic photosensitive member according to the present invention in a thickness direction.

FIG. 2 is a cross-sectional view in which the electrophotographic photosensitive member according to the present invention is enlarged in the thickness direction.

FIG. 3 is a cross-sectional view in which the electrophotographic photosensitive member according to the present invention is enlarged in the thickness direction.

FIG. 4 is a cross-sectional view in which the electrophotographic photosensitive member according to the present invention is enlarged in the thickness direction.

FIG. 5 is a cross-sectional view in which the electrophotographic photosensitive member according to the present invention is enlarged in the thickness direction.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Conductive support 2, 2 ', 2' ', 2' '', 2 '' '' ... Photosensitive layer 3 ... Charge generating substance 4 ... Charge carrier medium or charge carrier layer 5 ... Charge generating layer 6 ... Protection layer

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tamotsu Ariga 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Hiroshi Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Company Ricoh

Claims (1)

[Claims] 1. An electron comprising a conductive support and a photosensitive layer containing, as an active ingredient, at least one olefin compound having a pyrenyl group represented by the following general formula (I) (Formula 1). Photoreceptor for photography. [Chemical 1] (In the above formula, R ₁ and R ₂ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted phenyl group, and are the same. Or they may be different R
₃ , R ₄ represent a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different. R ₅ represents a hydrogen atom, a lower alkyl group or an alkoxy group. W is a hydrogen atom, a substituted or unsubstituted alkyl group, a phenylthio group, a chain unsaturated hydrocarbon group divalent group, a substituted or unsubstituted carbocyclic aromatic group monovalent group or divalent group, substituted or It represents a monovalent group or a divalent group of an unsubstituted heterocyclic group. j is 1 to 5, k is 1 to 4, l
Is an integer of 0 to 2, m is 1 or 2, and n is an integer of 1 to 3. When j, k, or n is 2 or more, R ₁ , R ₂ , R
₅ may be the same or different. )