JP2000214615A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment useful as an organic photoconductor used for a laminated photoreceptor by forming a photosensitive layer containing a specified tetraazaporphyrin compound as an organic pigment on a conductive substrate. SOLUTION: The photosensitive layer of the photoreceptor formed on a conductive substrate contains the tetraazaporphyrin pigment represented by formula in which M is an H atom or an atom or atomic group capable of forming covalent or coordination bond with the tetraazaporphyrin; each of R1-R4 is, independently, an H or halogen atom or a lower alkyl group. This pigment of the formula is used as the charge generating material for the electrophotographic photoreceptor in combination with a charge transport material in a functionally separate type or dispersed in the same layer. The charge generating material is added, preferably, in an amount of >=20 weight % of a binder in a charge generating layer, and the charge transport material is added, preferably, in an amount of 20-200 weight % of the binder in the charge transport layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreceptor for electrophotography, and more particularly, to a specific tetraazaporphyrin compound as a substance which generates charge carriers when irradiated with light (hereinafter referred to as "charge generating substance"). The present invention relates to an electrophotographic photosensitive member provided with a photosensitive layer containing the same.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as selenium, cadmium sulfide, and zinc oxide have been used as a photoconductive material of a photoreceptor used in an electrophotographic system.
The term "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place, for example, by corona discharge, and then subjected to image exposure to selectively dissipate the charges in only the exposed portions, and then statically. An image forming method in which an electrostatic latent image is obtained, and the latent image portion is developed and visualized with fine particles (toner) composed of a colorant such as a dye or a pigment and a polymer material to form an image. one of. The basic characteristics required of the photoreceptor in such an electrophotographic method include (1) being able to be charged to an appropriate potential in a dark place, (2) being less liable to dissipate electric charge in a dark place, and (3). The charge can be quickly dissipated by light irradiation. by the way,
At present, each of the above-mentioned inorganic substances has many advantages and also has various disadvantages.
For example, the selenium photoreceptor is difficult to manufacture, the manufacturing cost is high, it is difficult to process it into a belt because it is not flexible, and it needs to be handled with care because it is sensitive to heat and mechanical shock. There are also disadvantages. Cadmium sulfide and zinc oxide are dispersed in resin as a binder and used as photoreceptors.However, due to mechanical defects such as smoothness, hardness, tensile strength, and abrasion resistance, they are repeatedly used as they are. Can not be used. In recent years, electrophotographic photoreceptors using various organic substances have been proposed to eliminate the disadvantages of these inorganic substances, and some of them have been put to practical use. For example, a photoreceptor composed of poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one (described in U.S. Pat. No. 3,484,237), poly-N-vinylcarbazole is a pyrylium salt dye (Described in JP-B-48-25658), a photosensitive member containing an organic pigment as a main component (described in JP-A-47-37543), and a eutectic complex comprising a dye and a resin (Japanese Patent Application Laid-Open No. 47-10735)
No. 2, published in Japanese Unexamined Patent Publication (Kokai) Publication No. 2000-205, etc.). In particular, a laminated photoreceptor in which a thin film of an organic pigment is formed on a conductive support (a charge generation layer) and a layer mainly composed of a charge transport substance (a charge transport layer) is formed thereon is a conventional organic photoconductor. Active studies have been made on the basis of high sensitivity as compared with the photoreceptor and the wide variety of materials, and the photoreceptor is becoming a mainstay as a photoreceptor for copying machines and printers. However, speeding up the copier,
Or, considering the requirements for the photoreceptor, such as increasing the sensitivity in the wavelength range of the semiconductor laser, there is still no situation in which those requirements are sufficiently satisfied.

On the other hand, in the copying industry, in recent years, for high image quality, an editing function and a complex processing function have been required. Along with this, non-impact printer technology has been developed, and recording apparatuses have been widely used in digital systems such as laser printers, laser facsimile machines, and digital copying machines. As a light source used in the digital recording device, small, inexpensive, in terms of simplicity, etc.,
In many cases, a semiconductor laser is used, but the oscillation wavelength of a semiconductor currently used is limited to a wavelength region of 600 nm or more. Therefore, at least 600 to 850 of the electrophotographic photoreceptor used in these apparatuses is required.
It is required to have photosensitivity in the wavelength region of nm.

As organic photoconductive materials satisfying this requirement, phthalocyanine pigments, azo pigments, cyanine pigments, azulene pigments, squarium pigments and the like are known.
In particular, phthalocyanine pigments have spectral absorption up to a relatively long wavelength region, have photosensitivity, and have various variations depending on the type of central metal and crystal form. Research is being actively conducted. Known phthalocyanine pigments include ε-type copper phthalocyanine, X-type metal-free phthalocyanine, τ-type metal-free phthalocyanine, vanadyl phthalocyanine, titanyloxyphthalocyanine (JP-A-8-231869, JP-A-8-66595, JP-A-8-66595, 8-13942) and the like, but none of them are still sufficient in sensitivity, charging ability and repetition durability, and further improvements have been desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic photosensitive member which can be practically used not only for a high-speed copying machine but also for a laser printer, and particularly useful as an organic photoconductor used for a laminated photosensitive member. An object of the present invention is to provide a pigment, and to provide an electrophotographic photosensitive member having a layer containing the pigment as an active ingredient.

[0006]

According to the present invention, there is provided a tetraazaporphyrin compound represented by the following general formula (I) as an organic pigment:

[0007]

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(In the general formula (I), M represents a hydrogen atom or an atom or a compound capable of forming a covalent bond or a coordination bond with tetraazaporphyrin, and R1 to R4 are the same or different and represent a hydrogen atom, a lower alkyl group, Or a halogen atom.) Is formed on the photosensitive layer.

As the organic pigment used in the present invention, in addition to the organic pigment represented by the above general formula (I), for example, CI Pigment Blue 25 (Color Index Cl)
21180), C.I. Pigment Red 41 (Cl
21200), CI Acid Red 52 (Cl
45100), CI Basic Red 3 (Cl45
210), an azo pigment having a carbazole skeleton (described in JP-A-53-95033), an azo pigment having a distyrylbenzene skeleton (JP-A-53-133445), and an azo pigment having a triphenylamine skeleton ( JP-A-53-132347), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (JP-A-54-12742) Azo pigments having a fluorenone skeleton (described in JP-A-54-22834), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), and distyryloxadiazole skeleton. Azo pigments (JP-A-54-21)
No. 29), an azo pigment having a distyrylcarbazole skeleton (described in JP-A-54-14967)
Azo pigments such as C.I. Pigment Blue 1
6 (Cl 74100), phthalocyanine-based pigments such as titanyl phthalocyanine, for example, Sea Ivat Brown 5 (Cl 73410), Sea Ivat Dye (C
l 73030) and one or more perylene pigments such as Argoscarette B (manufactured by Bayer) and Inherence Scarlet R (manufactured by Bayer) with the pigment of the above general formula (I). You may use together.

Particularly, in the compound having a tetraazaporphyrin skeleton represented by the above general formula (I) and used in the present invention, M represents a hydrogen atom, Ti, Co, Ni,
Cu, Al, V, In, Cr, Ga, Ge and Mg atoms, or oxides or halides such as fluorides, chlorides, bromides and iodides thereof, and hydroxides thereof. Specifically, a hydrogen atom, Ti = O, Co, Cu, AlC
1, V = 0, InCl, Cr, GaCl, GaOH, G
or the like can be mentioned eCl _2, Mg. R1, R2
Are the same or different.Hydrogen atoms and lower alkyl groups represent straight-chain or branched alkyl groups such as methyl group, ethyl group, propyl group and butyl group.Halogen atoms include fluorine atom and chlorine Atom, bromine atom. Specific examples include the compounds shown in Table 1, but are not limited thereto.

[0011]

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[0012]

[Table 1]

[0013]

[Table 2]

[0014]

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The synthesis of the tetraazaporphyrin compound represented by the general formula (I) of the present invention can be carried out, for example, by using the corresponding 2,2
A 3-dicyanobenzo [1,4] dithiin derivative (the above general formula II) and a metal chloride or an alkoxy metal can be used without solvent or in a halogen-based solvent such as α-chloronaphthalene, dichlorobenzene, trichlorobenzene, or pentanol. ,
It can be obtained by heating in the presence of an alcohol solvent such as octanol, an amine solvent such as N, N-dimethylformamide and N-methylpyrrolidone, and an aromatic solvent such as benzene, toluene and nitrobenzene. Further, if necessary, the compound can be synthesized in the presence of an amine such as urea and formamide as a catalyst. The reaction temperature is usually from room temperature to 300 ° C, especially from 100 ° C to 200 ° C.
Is preferred in terms of reaction yield and purity.

The tetraazaporphyrin compound represented by the formula (I) is a corresponding 2,3-dicyanobenzo [1,
4] Instead of the dithiin derivative (II), the compound can be synthesized in the presence of a corresponding acid anhydride, a metal chloride, and an amine such as urea, formamide, ammonium molybdate as a catalyst. The reaction is usually carried out without solvent, a halogen-based solvent such as α-chloronaphthalene, dichlorobenzene, trichlorobenzene, an alcohol-based solvent such as pentanol and octanol, N, N-dimethylformamide,
It can be obtained by heating in the presence of an amine solvent such as N-methylpyrrolidone and an aromatic solvent such as benzene, toluene and nitrobenzene. The reaction temperature is usually from room temperature to 300 ° C., particularly preferably from 100 ° C. to 250 ° C., from the viewpoint of reaction yield and purity.

A dispersion type or function-separated type electrophotographic photoreceptor can be prepared by using the organic pigment represented by the general formula (I) of the present invention as a charge generating material and combining it with a charge transporting material. In the case of a dispersion type as a layer configuration, on a conductive substrate,
A photosensitive layer in which a charge generating substance and a charge transporting substance are dispersed in a binder is provided. In the case of the function-separated type, an electrophotographic photosensitive member having a charge generation layer composed of a charge generation substance on a substrate and a charge transport layer composed of a charge transport substance thereon is formed. Is formed, the charge generation layer and the charge transport layer may be stacked in reverse order.

Further, an intermediate layer may be provided between the photosensitive layer and the substrate in order to improve adhesion and charge blocking properties. Further, a protective layer may be provided on the photosensitive layer in order to improve mechanical durability such as friction resistance. The charge generating substance can be provided by dissolving or dispersing it in a suitable solvent together with a binder resin, if necessary, coating and drying.

Examples of the method for dispersing the charge generating substance include a ball mill, ultrasonic wave, and a homomixer.
Examples of the coating means include a dipping coating method, a blade coating method, and a spray coating method. When the charge generation material is dispersed to form a charge generation layer, the charge generation material is 2 μm in order to improve dispersibility in the layer.
The particles having an average particle size of 1 μm or less are preferable.

However, if the above-mentioned particle size is too small, the particles tend to agglomerate rather, increasing the resistance of the layer, reducing the sensitivity and repetition characteristics due to an increase in crystal defects, or limiting the miniaturization. , The lower limit of the average particle size is 0.0
It is preferably 1 μm. Examples of the solvent used when preparing the dispersion or solution of the charge generation layer or the charge transport layer include N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1 -Trichloroethane, dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate and the like.

As the binder used for forming the charge generating layer, the charge transport layer and the dispersion type photosensitive layer, any known binder having good insulating properties for an electrophotographic photosensitive member can be used. There is no limitation.

For example, polyethylene, polyvinyl butyral, polyvinyl formal, polysterene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, Polycarbonate resin, polyamide resin, silicone resin, addition polymerization type resin such as melamine resin, polyaddition type resin, polycondensation type resin, and copolymer resin containing two or more of repeating units of these resins, for example, vinyl chloride -Insulating resins such as vinyl acetate copolymer, sterene-acrylic copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and poly-N
Polymer organic semiconductors such as vinyl carbazole. These binders can be used alone or as a mixture of two or more.

In the case where a photoreceptor is prepared using the above-described layer constitution and substance, there are preferable ranges for the film thickness and the ratio of the substance. In the case of the negative charge type (lamination of the substrate / charge generation layer / charge transport layer), a binder is used as necessary in the charge generation layer. In this case, the ratio of the charge generation substance to the binder is 20% by weight. As described above, the thickness is preferably 0.01 to 5 μm. In the charge transport layer, the ratio of the charge transport material to the binder is 20 to 200% by weight or more, and the film thickness is 5 to 100%.
It is preferably set to μm. In the case of the positive charge type, the ratio of the charge transport material to the binder is 20 in the charge transport layer.
It is preferable that the film thickness be 5 to 100 μm and the film thickness be 5 to 100 μm.

The charge generating layer preferably contains a charge generating substance in an amount of 20% by weight or more based on the binder. Further, the charge generation layer preferably contains a charge transporting substance, which has the effect of suppressing residual potential and improving sensitivity. In this case, the charge transporting material is preferably contained in an amount of 20 to 200% by weight based on the binder. In the case of a so-called dispersion type photoconductor in which a charge generating material and a charge transporting material are dispersed in a binder resin, the ratio of the pigment as the charge generating material to the binder resin in the photosensitive layer is as follows. 5 to 95% by weight, film thickness 10 to 100 μm
It is preferred that In this case, the ratio of the charge transporting substance to the binder resin is preferably 30 to 200% by weight.

Further, in the above-mentioned photosensitive layer, a phenol compound, a hydroquinone compound, a hindered phenol compound, a hindered amine compound, a hindered amine and a hindered phenol are used for the purpose of improving the chargeability and the like.
Compounds existing in the same molecule can be added.

In the present invention, examples of the conductive substrate include metal plates such as aluminum, nickel, copper, titanium, gold, and stainless steel, metal drums or metal foils, aluminum, nickel, copper, titanium, gold tin oxide, and indium oxide. Or a film or a drum of plastic or the like, or a paper or plastic coated with a conductive substance.

If necessary, an undercoat is used on a conductive substrate. In this case, the undercoat layer may be made of polyamide resin, polyvinyl alcohol, ethylcellulose, or the like in addition to the binder resin described above. Carboxymethylcellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, N-alkoxymethyl nylon, etc., without any resin, or tin oxide, aluminum oxide, titanium oxide, silicon oxide Alternatively, a vapor-deposited film of aluminum oxide, zinc oxide, titanium oxide, silicon oxide, or the like can be given.

Further, as the material used for the protective layer, it is appropriate to use the above-mentioned resin as it is, or to disperse a low-resistance substance such as tin oxide or indium oxide. Further, an organic plasma polymerized film can be used, and the organic plasma polymerized film may appropriately contain oxygen, halogen, and atoms of Group III and Group V of the periodic table as needed.

The charge transport material includes a hole transport material and an electron transport material. As the hole transport material, for example, poly-N
Carbazole and its derivatives, poly-γ-carbazolylethyl glutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene,
There are polyvinylphenanthrene, oxazole derivatives, imidazole derivatives, triphenylamine derivatives, and compounds represented by the following general formula.

(1) (described in JP-A-55-154955 and JP-A-55-156954)

[0031]

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(Wherein R ¹ is a methyl group, an ethyl group, 2-
Represents a hydroxyethyl group or a 2-chloroethyl group,
R ² represents a methyl group, an ethyl group, a benzyl group or a phenyl group; R ³ represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
Represents a dialkylamino group or a nitro group. (2) (described in JP-A-55-52063)

[0033]

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(Wherein, Ar represents a naphthalene ring, an anthracene ring, a styryl ring or a substituted product thereof, or a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group). (Described in JP-A-56-81850)

[0035]

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Wherein R ¹ is an alkyl group, a benzyl group,
Represents a phenyl group or a naphthyl group, R ² is a hydrogen atom,
Represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a diaralkylamino group or a diarylamino group, and n represents an integer of 1 to 4,
When n is 2 or more, R ² may be the same or different. R ³ represents a hydrogen atom or a methoxy group. (4) (described in JP-B-51-10983)

[0037]

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(Wherein R ¹ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group; R ² and R ³ may be the same or different; Represents an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group, a chloroalkyl group or a substituted or unsubstituted aralkyl group, and R ² and R ³ may be bonded to each other to form a nitrogen-containing heterocyclic ring. R ⁴ may be the same or different and represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom.) (5) (described in JP-A-51-94829)

[0039]

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(In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group or carbazolyl group.) (6) (JP-A-52-128373) In the gazette)

[0041]

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(Wherein R ¹ is a hydrogen atom, a halogen atom,
Cyano group, alkoxy group having 1 to 4 carbon atoms or 1 carbon atom
Represents an alkyl group of 4 to 4, wherein Ar is

[0043]

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R ² represents an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom, a halogen atom, and a C 1 to C 4
Wherein n is 1 or 2, and when n is 2, R ³ may be the same or different, and R ⁴ , R ^4
5 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms or a substituted or unsubstituted benzyl group. (7) (described in JP-A-56-29245)

[0045]

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(Wherein R is a carbazolyl group, a pyridyl group, a thienyl group, an indolyl group, a furyl group or a substituted or unsubstituted phenyl group, a styryl group, a naphthyl group, or an anthryl group. Is a dialkylamino group, an alkyl group, an alkoxy group,
Represents a group selected from the group consisting of a carboxy group or an ester thereof, a halogen atom, a cyano group, an aralkylamino group, an N-alkyl-N-aralkylamino group, an amino group, a nitro group and an acetylamino group. (8) (described in JP-A-58-58552)

[0047]

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(Wherein R ¹ represents a lower alkyl group, a substituted or unsubstituted phenyl group or a benzyl group;
² represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group or an amino group substituted with a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2. (9) (described in JP-A-57-73075)

[0049]

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(Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ² and R ³ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group. , R ⁴ represents a hydrogen atom, a lower alkyl group or a substituted or unsubstituted phenyl group, also, Ar represents a substituted or unsubstituted phenyl group or a naphthyl group.) (10) (JP-a-58-198043 In the gazette)

[0051]

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Wherein n is an integer of 0 or 1, R ¹ is a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group, Ar ¹ is a substituted or unsubstituted aryl group, and R ⁵ is A represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group;

[0053]

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Represents a 9-anthryl group or a substituted or unsubstituted carbazolyl group, wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or

[0055]

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(Provided that R ³ and R ⁴ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, R ³ and R ⁴ may be the same or different, and R ⁴ is May form a ring)
When m is 2 or more, R ² may be the same or different. When n is 0, A and R ¹ may form a ring together. (11) (described in JP-A-49-105537)

[0057]

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(Wherein R ¹ , R ² and R ³ are hydrogen atoms,
Represents a lower alkyl group, a lower alkoxy group, a halogen atom or a dialkylamino group, and n represents 0 or 1. (12) (described in JP-A-52-139066)

[0059]

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(Wherein R ¹ and R ² represent an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group or an allyl group. (13) (described in JP-A-52-139065)

[0061]

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(Wherein X represents a hydrogen atom, a lower alkyl group or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted (It represents an unsubstituted aryl group.) (14) (described in JP-A-58-32372)

[0063]

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(Wherein, R ¹ represents a lower alkyl group, a lower alkoxy group or a halogen atom, n represents an integer of 0 to 4, R ² and R ³ may be the same or different, and represent a hydrogen atom, It represents a lower alkyl group, a lower alkoxy group or a halogen atom.) (15) (correctly described in JP-A-2-178669)

[0065]

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(Wherein R ¹ , R ³ and R ⁴ are hydrogen atoms,
An amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom or a substituted or unsubstituted aryl group, R ² is a hydrogen atom, an alkoxy group, a substituted or Represents an unsubstituted alkyl group or a halogen atom.
However, the case where all of R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms is excluded. Also, k, 1, m and n are 1, 2, 3
Or, when each is an integer of 2, 3 or 4, R ¹ , R ² , R ³ and R ⁴ may be the same or different. (16) (Recorded in JP-A-3-285960)

[0067]

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(Wherein, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms, and R ¹ and R ² represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group,
Represents an alkoxy group or a substituted or unsubstituted phenyl group, which may be the same or different; (17) (described in Japanese Patent Application No. 62-98394) A-CH = CH-Ar-CH = CH-A (wherein Ar represents a substituted or unsubstituted aromatic hydrocarbon group) And A is

[0069]

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(Where Ar ¹ represents a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ and R ² represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group). (18) (described in JP-A-4-230766)

[0071]

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(Wherein, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. N represents 0 or 1) , M is 1 or 2, and n =
When 0 and m = 1, Ar and R may form a ring together. Examples of the compound represented by the general formula 11 include 9-ethylcarbazole-3-aldehyde-1-methyl-1-phenylhydrazone and 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone. , 9-
Ethylcarbazole-3-aldehyde-1,1-diphenylhydrazone and the like. Compounds represented by general formula 12 include, for example, 4-diethylaminostyryl-β-aldehyde-1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenyl There is a hydrazone.

Compounds represented by general formula 13 include, for example, 4-methoxybenzaldehyde-1-methyl-1-
Phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1- (4-
Methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1
-Diphenylhydrazone and the like.

Compounds represented by general formula 14 include, for example, 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4 -Dibenzylaminophenyl) propane and 2,2'-dimethyl-4,4'-bis (diethylamino) -triphenylmethane.

The compounds represented by the general formula 15 include, for example, 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene. Examples of the compound represented by the general formula 16 include 9- (4-dimethylaminobenzylidene) fluorene and 3- (9-fluorenylidene) -9-ethylcarbazole. Examples of the compound represented by the general formula 18 include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis (2,4-dimethoxystyryl) benzene.

Compounds represented by the general formula 19 include, for example, 3-styryl-9-ethylcarbazole, 3- (4
-Methoxystyryl) -9-ethylcarbazole and the like. Compounds represented by general formula 20 include, for example, 4
-Diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4
-Diphenylaminostyryl) naphthalene, 1- (4-
And diethylaminostyryl) naphthalene.

The compound represented by the general formula 21 includes, for example, 4'-diphenylamino-α-phenylstilbene, 4'-bis (4-methylphenyl) amino-α-phenylstilbene and the like. Examples of the compound represented by the general formula 23 include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) virazoline and the like.

The compound represented by the general formula (24) includes, for example, 2,5-bis (4-diethylaminophenyl)-
1,3,4-oxadiazole, 2-N, N-diphenylamino-5- (4-diethylaminophenyl) -1,
3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl)-
1,3,4-oxadiazole and the like. General formula 2
Compounds represented by 5 include, for example, 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- (4-diethylaminophenyl) ) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole.

The benzidine compound represented by the general formula 26 includes, for example, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl]-
4,4′-diamine, 3,3′-dimethyl-N, N,
N ', N'-tetrakis (4-methylphenyl)-
[1,1′-biphenyl] -4,4′-diamine and the like. The biphenylamine compound represented by the general formula 27 includes, for example, 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine, 4′-
Methyl-N, N-bis (4-methylphenyl)-[1,
1'-biphenyl] -4-amine, 4'-methoxy-
N, N-bis (4-methylphenyl)-[1,1′-biphenyl] -4-amine and the like.

Examples of the triarylamine compound represented by the general formula 28 include 1-diphenylaminopyrene and 1-di (p-tolylamino) pyrene.
Examples of the diolefin aromatic compound represented by the general formula 29 include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl. Benzene.

Examples of the styrylpyrene compound represented by the general formula 30 include 1- (4-diphenylaminostyryl) pyrene and 1- [4-di (p-tolyl) aminostyryl] pyrene. In addition, as an electron transport substance, for example, chloranil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7
-Trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro -Indeno-4H-indeno [1,2-b] thiophen-4-one, 1,3,7
-Trinitrodibenzothiophene-5,5-dioxide and the like.
The electron transporting substances listed in Formula 33 can be suitably used. These charge transport materials are used alone or in combination of two or more.

[0082]

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[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to Production Examples and Examples, but the present invention is not limited to these Production Examples and Examples.

Production Example 1 0.73 g (30 mmol) of magnesium and a catalytic amount of iodine were added to 80 ml of 1-pentanol. The mixture was heated to reflux temperature, stirred and mixed for 2 hours under a nitrogen stream, and then allowed to cool.
At room temperature, 4.33 g (20 mmol) of 2,3-dicyanobenzo [1,4] dithiin was added, and the mixture was stirred and reacted under reflux for 5 hours. After completion of the reaction, the reaction mixture was filtered while hot, washed sufficiently with ethanol and ion-exchanged water, and dried to obtain 4.33 g (yield 97.5%) of Mg tetraazaporphyrin pigment. From the results of the following elemental analysis, it was confirmed that the obtained pigment was a Mg tetraazaporphyrin compound.

[0085]

[Table 3]

Production Example 2 4.33 g of the Mg tetraazaporphyrin pigment obtained in Production Example 1 was added little by little to 50 ml of sulfuric acid kept at 5 ° C. or lower in an ice bath and stirred and mixed for 4 hours. The mixed solution was poured into 500 ml of ion-exchanged water kept at 5 ° C. or lower in an ice bath,
Stir for 2 hours and leave overnight. After that, it was filtered and washed thoroughly with ethanol and ion-exchanged water. After drying, 3.47 g (80% yield) of a metal-free tetraazaporphyrin pigment was obtained. FIG. 1 shows the IR spectrum. From the results of the following elemental analysis, it was confirmed that the obtained pigment was a metal-free tetraazaporphyrin compound.

[0087]

[Table 4]

Production Example 3 2,3-dicyano-benzo [1,4] dithiin 4.33
g (10 mmol), titanium tetra-n-butoxide 3.40 g (10 mmol), urea 0.6 g (10 m
mol) was added to 80 ml of 1-octanol, and the mixture was stirred and reacted at 150 ° C. for 5 hours under a nitrogen stream. After the completion of the reaction, the mixture was filtered while hot, and sufficiently washed with ethanol and water. After drying, 1.74 g (yield 75%) of crude titanium oxytetraazaporphyrin pigment was obtained. 1.74 g of the obtained crude titanium oxytetraazaporphyrin pigment was added little by little to 52 ml of trifluoroacetic acid kept at 5 ° C. or lower in an ice bath and stirred and mixed for 4 hours. The mixed solution is ion-exchanged water 104 kept at 5 ° C. or lower in an ice bath.
Pour into 0 ml, stir for 2 hours and leave overnight. afterwards,
The mixture was filtered, sufficiently washed with ethanol and ion-exchanged water, and dried to obtain 1.29 g (yield: 55.5%) of titanium oxytetraazaporphyrin pigment. FIG. 2 shows the IR spectrum. From the results of the following elemental analysis, it was confirmed that the obtained pigment was a titanium oxytetraazaporphyrin compound.

[0089]

[Table 5]

Example 1 1 part by weight of the compound obtained in Production Example 2 was 2% by weight of a polyvinyl butyral resin (Eslex BMS: manufactured by Sekisui Chemical).
50 parts of a butyl acetate solution, 49 parts of n-butyl acetate
Dispersion was performed for 2 hours with a sand mill using mmφ glass beads to prepare a charge generation layer coating solution. The coating solution thus prepared was applied on a 75 μm aluminum-deposited PET base, and dried at 80 ° C. for 5 minutes to form a charge generation layer having a thickness of 0.2 μm.

Next, 60 parts of a charge transport material having the following structural formula:
60 parts of a polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) and 0.001 parts of silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 680 parts of dichloromethane to prepare a coating solution for a charge transport layer. This was applied on the charge generation layer and dried at 80 ° C. for 5 minutes and at 110 ° C. for 10 minutes to form a charge transport layer having a thickness of 20 μm.
Was obtained.

[0092]

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Example 2 The same procedure as in Example 1 was repeated except that the following compound was used instead of the charge transporting substance used in Example 1, and the photosensitive member No.
2 was produced.

[0094]

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Example 3 The same procedure as in Example 1 was repeated except that the following compound was used instead of the charge transporting substance used in Example 1, and the photosensitive member No.
3 was produced.

[0096]

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Example 4 The same procedure as in Example 1 was repeated except that the following compound was used instead of the charge transporting substance used in Example 1, and the photosensitive member No.
4 was produced.

[0098]

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Example 5 A photoconductor No. 5 was prepared in the same manner as in Example 1 except that the compound obtained in Production Example 3 was used. Example 6 A photoconductor No. 6 was prepared in the same manner as in Example 2 except that the compound obtained in Production Example 3 was used. Example 7 Photoconductor No. 7 was prepared in the same manner as in Example 3, except that the compound obtained in Production Example 3 was used.

Example 8 Photoconductor No. 8 was prepared in the same manner as in Example 4 except that the compound obtained in Production Example 3 was used. (Evaluation) The photoconductors manufactured in Examples 1 to 8 were measured at -6 kV using an electrostatic property measuring device EPA-8200 manufactured by Kawaguchi Electric Co., Ltd.
In allowed charging by performing corona discharge for 20 seconds, followed by 20 seconds the surface potential Vo after being dark decay (V), after irradiation of the 20 lux, Vo is the exposure required to be 1/2 E _{1 / 2}
(Lux · Sec) was measured. Table 2 shows the results.

[0101]

[Table 6]

Example 9 In the same manner as in Example 1, a charge generation layer was formed on an aluminum-deposited PET base. Next, 64 parts by weight of an electron transport material having the following structural formula (Formula 31), 96 parts of a polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 0.001 part by weight of silicon oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed with tetrahydrofuran. This was dissolved in 640 parts by weight, and this was applied onto the charge generation layer by casting with a doctor blade, and dried to form a charge transport layer having a thickness of 20 μm. Thus, Photoconductor No. 9 was manufactured.

[0103]

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Example 10 A photoconductor No. 10 was manufactured in the same manner as in Example 9 except that the electron transporting material used in Example 9 was replaced by an electron transporting material having the following structural formula (Formula 32). did.

[0105]

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Example 11 Photosensitive member No. 11 was prepared in the same manner as in Example 9, except that the electron transporting material used in Example 9 was replaced by an electron transporting material having the following structural formula (Formula 33). .

[0107]

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The photoreceptors produced in Examples 9 to 11 were charged by performing a corona discharge at +5.3 kV for 20 seconds using the above-described measuring apparatus, and subsequently a surface potential Vo (V) after being dark-decayed for 20 seconds. ), After irradiation with light of 20 lux, Vo is １ ／
The amount of exposure _1/2 (lux · Sec) required to be measured. Table 3 shows the results.

[0109]

[Table 7]

Example 12 10 g of a solution of 0.5 g of the compound obtained in Production Example 2 in a polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company)
After ball milling with 9 g of tetrahydrofuran (dissolved to a concentration of 10% by weight in tetrahydrofuran), the pigment composition was 2% by weight, and the polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) was 50% by weight. A solution of 10% by weight of a polycarbonate resin (Iupilon Z200: manufactured by Mitsubishi Gas Chemical Company) was added so that the charge transporting substance used in Example 4 was 28% by weight, and the mixture was sufficiently stirred to prepare a photosensitive layer forming solution. . The coating solution prepared in this way was applied to a polyester film on which aluminum was deposited by a doctor blade, and a single-layer type electrophotographic photoreceptor No. 12 having a photosensitive layer having a thickness of 15 μm after drying was obtained. Made.

The photoreceptor prepared in Example 12 was charged by performing a corona discharge at +6 kV for 20 seconds using the above-described measuring apparatus, and subsequently, the surface potential Vo after being darkly attenuated for 20 seconds.
(V) After irradiation with 20 lux of light, the exposure amount E _1/2 (lux · Sec) required to reduce Vo to １ ／ was measured. Table 4 shows the results.

[0112]

[Table 8]

[0113]

The photoreceptor containing the tetraazaporphyrin compound according to the present invention has a laminated negative charging type, a laminated positive charging type,
The single-layer type has excellent electrophotographic properties.

[Brief description of the drawings]

FIG. 1 is an IR spectrum diagram of a metal-free tetraazaporphyrin pigment obtained in Production Example 2.

FIG. 2 is an IR spectrum of the titanium oxytetraazaporphyrin pigment obtained in Production Example 3.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kaoru Tadokoro 1-36 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (Reference) 2H068 AA19 AA21 AA31 AA33 AA34 AA37 BA38 BA39 FC02 FC03

Claims (4)

[Claims] An electrophotographic photoreceptor comprising a photosensitive layer containing, as an active ingredient, a tetraazaporphyrin compound represented by the following general formula (I) on a conductive support. Embedded image (In the general formula (I), M represents a hydrogen atom or an atom or a compound capable of forming a covalent bond or a coordination bond with tetraazaporphyrin, and R1 to R4 are the same or different and represent a hydrogen atom, a lower alkyl group, or a halogen atom. Represents.) 2. A layered electrophotographic photosensitive member comprising a conductive support and a charge generation layer containing a charge generation material and a charge transfer layer containing a hole transport material sequentially provided on the charge generation layer. An electrophotographic photoreceptor comprising a compound represented by the above general formula (I). 3. A layered electrophotographic photosensitive member in which a charge generating layer containing a charge generating substance and a charge transfer layer containing an electron transporting substance are sequentially provided on a conductive support, wherein the charge generating layer is provided on the charge generating layer. An electrophotographic photoreceptor comprising a compound represented by the general formula (I): 4. A single-layer type electrophotograph, wherein the photosensitive layer according to claim 1 is a single layer containing at least a compound represented by the general formula (I) according to claim 1 as a charge generating substance. Photoconductor.