JP2000003053A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated electrophotographic photoreceptor, which can be put to practical use as a photoreceptor for a high-speed copying machine or a laser printer. SOLUTION: The electrophotographic photoreceptor has a layer contg. a compd. having a tetraazaporphyrin skeleton represented by the formula as an effective component. In the formula, M is H or an atom or compd. capable of covalent bonding or coordinate bonding to tetraazaporphyrin and R1-R4 are each H, a lower alkyl or aryl.

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 photoreceptor having a specific tetraazaporphyrin skeleton 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 a compound having 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 an electro-detection fine particle (toner) composed of a colorant such as a dye or a pigment and a polymer material to form an image. One. 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. 139, pp. 139- 139), the representative of which is classified according to the sensitization method. 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, the speed of the Shengsha machine,
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 laser printers, laser facsimile machines,
2. Description of the Related Art Recording devices are becoming widespread in digital systems such as digital copying machines. As a light source used in the digital recording apparatus, a semiconductor laser is often used in terms of small size, low cost, simplicity, and the like, but the oscillation wavelength of a semiconductor currently used has a wavelength of 600 nm or more. Limited to the area. Therefore, at least 600 to 8 electrophotographic photosensitive members used in these apparatuses are used.
It is required to have photosensitivity in a wavelength region of 50 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 An object of the present invention is to provide a photosensitive material for electrophotography 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. Another object of the present invention is to provide an electrophotographic photoreceptor having a layer containing the pigment as an active ingredient.

[0006]

According to the present invention, there is provided a pigment characterized in that the organic pigment is a compound having a tetraazaporphyrin skeleton represented by the general formula (I),

[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 coordinate bond with tetraazaporphyrin, and R ¹ , R ² , R ³ and R ⁴ are the same or different. , A hydrogen atom, a lower alkyl group, or a substituted or unsubstituted aryl group.) Further, there is provided an electrophotographic photoreceptor characterized by forming a layer having the pigment.

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 CI)
21180), C.I. Pigment Red 41 (CI2
1200), CI Acid Red 52 (CI461)
00), CI Basic Red 3 (CI4521)
0), an azo pigment having a carbazole skeleton (JP-A-53
95033), an azo pigment having a distyrylbenzene skeleton (Japanese Patent Application Laid-Open No. 53-133445), an azo pigment having a triphenylamine skeleton (described in Japanese Patent Application Laid-Open No. 53-132347), dibenzothiophene Azo pigments having a skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), and azo pigments having a fluorenone skeleton (described in JP-A-54-12742) No. 22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), and an azo pigment having a distyryloxadiazole skeleton (described in 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 (CI74100), phthalocyanine-based pigments such as titanyl phthalocyanine, for example, Sea Ivat Brown 5 (CI73410), Sea Ivat Die (CI7
3030), Argoscarlet B (manufactured by Bayer AG), Intrance Scarlet R
(Manufactured by Bayer AG) and the like. These organic pigments may be used alone or in combination of two or more.

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, Mg atoms, or oxides or halides such as fluoride, chloride, bromide and iodide thereof, and hydroxides thereof. R
¹ , R ² , R ³ , and R ⁴ are the same or different, and represent a hydrogen atom or a lower alkyl group as a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; The substituent represents a fluorine atom, a halogen atom such as a chlorine atom, and the substituted or unsubstituted aryl group represents an aryl group such as a phenyl group, a naphthyl group, a pyrenyl group, and the substituent is a fluorine atom. ,
Represents a halogen atom such as a chlorine atom and an alkyl group such as a methyl group and an ethyl group. Specific examples include those shown in Table 1, but are not limited thereto.

[0011]

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[0012]

[Table 1]

In the synthesis of the tetraazaporphyrin compound represented by the general formula (I) of the present invention, for example, a corresponding dinitrile compound and a metal chloride or an alkoxy metal are prepared by using no solvent or α-chloronaphthalene or dichlorobenzene. In the presence of halogenated solvents such as benzene, trichlorobenzene and the like, alcohol solvents such as pentanol and otatanol, amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone, and aromatic solvents such as benzene, toluene and nitrobenzene. And can be obtained by heating. The reaction temperature is usually from room temperature to 300 ° C., especially 100 ° C.
It is preferable to perform the reaction at a temperature of from 250C to 250C from the viewpoint of the reaction yield. The tetraazaporphyrin compound represented by the formula (1) can also be synthesized in the presence of a corresponding acid anhydride, a metal chloride, and an amine such as urea or ammonium molybdate as a catalyst.

The reaction is usually carried out in the absence of a solvent, a halogen-based solvent such as α-chloronaphthalene, dichlorobenzene and trichlorobenzene, an alcohol-based solvent such as pentanol and octanol, and an amine such as N, N-dimethylformamide and N-methylpyrrolidone. It can be obtained by heating in the presence of a system solvent, 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 the reaction yield.

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 separation type, a charge generation layer containing a charge generation substance and a binder is formed on a substrate, and a charge transport layer containing a charge transport substance and a binder is formed thereon. In this case, 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, an ultrasonic wave, and a homomixer, and examples of the application method 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, in order to improve dispersibility in the layer,
The charge generating substance preferably has an average particle diameter of 2 μm or less, preferably 1 μm or less. However, if the above-mentioned particle size is too small, it tends to agglomerate, the resistance of the layer increases, the crystal defects increase, the sensitivity and the repetition characteristics decrease, or there is a limit in miniaturization. The lower limit of the diameter is preferably set to 0.01 μm.

Examples of the solvent used for preparing the dispersion or solution of the charge generation layer or the charge transport layer include, for example,
N, N-dimethylformamide, toluene, xylene,
Monochlorobenzene, 1,2-dichloroethane, 1,
1,1-trichloroethane, dichloromethane, 1,1,
Examples thereof include 2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, and butyl acetate. As the binder used in forming the charge generation layer, the charge transport layer and the dispersion type photosensitive layer, any binder can be used as long as it is a conventionally known binder for an electrophotographic photosensitive member having good insulating properties, and is not particularly limited. .

For example, polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic resin, vinyl acetate 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, styrene-acryl 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 kinds.

In the case where a photoreceptor is prepared by using the above-mentioned 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 drag generator to the binder is 20% by weight. % Or more, and the film 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 contained 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, tin oxide gold, 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 layer may be used on the conductive substrate. In this case, the undercoat layer may be made of a polyamide resin, polyvinyl alcohol, ethyl cellulose, carboxy resin, or the like, in addition to the binder resin described above. Methylcellulose, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, casein, N-alkoxymethyl nylon, etc. as it is, or tin oxide, aluminum oxide, titanium oxide, silicon oxide, Alternatively, a deposition film of aluminum oxide, zinc oxide, titanium oxide, silicon oxide, or the like, in which indium oxide or the like is dispersed, and 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) General formula 1 (JP-A-56-15495)
No. 5, described in JP-A-55-156954)

[0028]

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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) General formula 2 (described in JP-A-55-52063)

[0030]

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(In the formula, 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.) 3 (described in JP-A-56-81850)

[0032]

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(Wherein R ¹ is an alkyl group, a pendyl 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) General formula 4 (described in JP-B-51-10983)

[0034]

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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. good.

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) General formula 5 (described in JP-A-51-94829)

[0037]

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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) General formula 6 (JP-A Sho 52) -128373)

[0039]

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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

[0041]

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

[0043]

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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) General formula 8 (described in JP-A-58-58552)

[0045]

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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) General formula 9 (described in JP-A-57-73075)

[0047]

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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, and Ar represents a substituted or unsubstituted phenyl group or a naphthyl group.) (10) Formula 10 (JP-A-58-1983) -198043)

[0049]

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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;

[0051]

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

[0053]

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[0054] (wherein, R ³ and R ⁴ represents an alkyl group, a substituted or unsubstituted置漁aralkyl group, or a substituted or unsubstituted aryl group, R ³ and R ⁴ may be the same or different, R ⁴ 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) General formula 11 (described in JP-A-49-105537)

[0055]

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

[0057]

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(Wherein R ¹ and R ² represent an alkyl group containing 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) General formula 13 (described in JP-A-52-139065)

[0059]

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(In the formula, 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 aryl group. (It represents an unsubstituted aryl group.) (14) General formula 14 (described in JP-A-58-32372)

[0061]

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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, Represents a lower alkyl group, a lower alkoxy group or a halogen atom.) (15) Formula 15 (described in JP-A-2-178669)

[0063]

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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. 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) General formula (described in JP-A-3-285960)

[0065]

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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) General formula 17 (described in JP-A-62-98394)

[0067]

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[Wherein, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and A represents

[0069]

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(However, Ar ′ represents a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ and R ² are a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.) . (18) General formula 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 1 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 2 include, for example, 4-diethylaminostyryl-β
-Aldehyde-1-methyl-1-phenylhydrazone,
4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone and the like.

The compound represented by the general formula 3 includes, for example, 4-methoxybenzaldehyde-1-methyl-1-
Phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-pendyl-1-phenylhydrazone, 4-diethylaminopentaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1- (4-
Methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1
-Diphenylhydrazone and the like.

The compounds represented by the general formula 4 include:
For example, 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl)
Examples include methane, 1,1-bis (4-dibenzylaminophenyl) propane, and 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane.
Compounds represented by general formula 5 include, for example, 9- (4-diethylaminostyryl) anthracene, 9-bromo-1
0- (4-diethylaminostyryl) anthracene and the like.

The compound represented by the general formula 6 includes
For example, 9- (4-dimethylaminobenzylidene) fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole, and the like can be given. Examples of the compound represented by the general formula 7 include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis (2,4-dimethoxystyryl) benzene.

Compounds represented by general formula 8 include, for example, 3-styryl-9-ethylcarbazole, 3- (4
-Methoxystyryl) -9-ethylcarbazole and the like. Compounds represented by general formula 9 include, for example, 4-
Diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-
Examples include diphenylaminostyryl) naphthalene and 1- (4-diethylaminostyryl) naphthalene.

The compound represented by the general formula 10 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 11 include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazolin.

Compounds represented by general formula 12 include, 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 1
Examples of the compound represented by 3 include 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole and 2- (4-diethylaminophenyl) ) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole.

The benzidine compound represented by the general formula 14 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. Examples of the biphenylamine compound represented by the general formula 15 include 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine and 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 16 include 1-diphenylaminopyrene, 1-di (p-tolylamino) pyrene, and the like.
Examples of the diolefin aromatic compound represented by the general formula 17 include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) aminostyryl. Benzene. The styrylpyrene compounds represented by the general formula (18) include, for example, 1- (4-diphenylaminostyryl) pyrene,
-[4-di (p-tolyl) aminostyryl] pyrene and the like.

Examples of the electron transporting substance include chloranil, bromanil, 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] Thiophene-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide and the like, and further, an electron transporting material represented by the following formula 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) 0.36 g of magnesium (1
5 mmol) and a catalytic amount of iodine in 1-pentanol 40
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 5,6-dihydro-P-dithiin-2,3-dicarbonitrile 1.68
g (10 mmol) was added, and the mixture was stirred and reacted for 5 hours while maintaining the reaction temperature at 150 ° C. After the completion of the reaction, perform hot filtration, wash thoroughly with ethanol and water,
After drying, 1.43 g (yield 82%) of Mg tetraazaporphyrin pigment was obtained. FIG. 1 shows the IR spectrum. From the results of the following elemental analysis, it was confirmed that the obtained crystals were Mg tetraazaporphyrin compounds.

[0085] (Production Example 2) 1.0 g (1.4 mmol) of the Mg tetraazaporphyrin pigment obtained in Production Example 1 was kept at 5 ° C or less in an ice bath, and added little by little to 20 ml of trifluoroacetic acid.
Stir and mix for 9 hours. After completion of the reaction, the mixture is kept at 5 ° C. or lower under an aqueous solution, poured into 800 ml of ion-exchanged water, and stirred for 2 hours.
After standing, the mixture was filtered, sufficiently washed with ethanol and water, and dried to obtain 0.70 g (yield 74%) of a metal-free tetraazaporphyrin pigment. FIG. 2 shows the IR spectrum. The obtained crystals were confirmed to be a metal-free tetraazaporphyrin compound from the results of the following elemental analysis.

[0086] Example 1 1 part by weight of the compound obtained in Production Example 1 and 2% by weight of a polyvinyl butyral resin (ESLEX BLS: 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 0.2 μm-thick charge generation layer.

Next, 42 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 silicon oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 638 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.

[0088]

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Example 2 The same procedure as in Example 1 was repeated except that the following compound was used in place of the charge transporting substance used in Example 1, and the photosensitive member N was used.
o. 2 was produced.

[0090]

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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.

[0092]

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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.

[0094]

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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 2 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 2 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 2 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 2 was used.

(Evaluation) The photoconductors prepared in Examples 1 to 8 were charged by performing a corona discharge at −6 kV for 20 seconds at −6 kV using an electrostatic property measuring device EPA-8200 manufactured by Kawaguchi Electric Co., Ltd.
Subsequently, the surface potential Vo (V) after dark decay for 20 seconds, 2
After the light irradiation of 0 lux, the exposure amount El _{/ 2} (lux · sec) necessary for reducing Vo to 1/2 was measured. Table 2 shows the results.

[0098]

[Table 2]

Example 9 In the same manner as in Example 1, a charge generation layer was formed on an aluminum-deposited PET base. Next, 8 parts by weight of an electron transporting substance having the following structural formula (Chemical Formula 31), 11 parts by weight of polycarbonate Z (manufactured by Teijin Chemicals Limited), and 0.02 parts by weight of silicone oil (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to 91 parts by weight of tetrahydrofuran. This was melted and cast onto the charge generating layer by a doctor blade, and dried to form a charge transporting layer having a thickness of 20 μm. Thus, photoreceptor No. 9 was prepared.

[0100]

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

[0102]

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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). .

[0104]

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The photoreceptors prepared 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, the surface potential Vo (V) after dark decay for 20 seconds. ), After exposure to 20 lux, the exposure amount E _{l / 2} (lux · sec) required to reduce Vo to _{１ ／} was measured. Table 3 shows the results.

[0106]

[Table 3]

Example 12 0.5 g of the compound obtained in Production Example 1 was used in polycarbonate Z
After ball milling with 10 g of a solution (manufactured by Teijin Chemicals Ltd. so as to have a concentration of 10% by weight in tetrahydrofuran) and 9 g of tetrahydrofuran, the pigment composition was 2% by weight and the PC-Z composition was 50% by weight. A 10% by weight polycarbonate Z solution was added so that the charge transporting substance used in Example 4 was 28%, and the mixture was sufficiently stirred to prepare a photosensitive layer forming solution. The coating solution prepared in this way was applied by casting with a doctor blade onto a polyester film on which aluminum had been deposited, and a single-layer type electrophotographic photoreceptor No. 12 having a photosensitive layer having a thickness of 15 μm after drying was obtained. Produced.

Example 13 Photoreceptor No. 13 was prepared in the same manner as in Example 12, except that the compound obtained in Production Example 2 was used. The photoreceptors prepared in Examples 12 and 13 were charged by performing a corona discharge at +6 kV for 20 seconds using the above-described measuring device, and subsequently, the surface potential Vo after being darkly attenuated for 20 seconds.
(V) After exposure to light of 20 lux, the exposure amount El _{/ 2} (lux · sec) necessary for reducing Vo by _{１ ／} was measured. Table 4 shows the results.

[0109]

[Table 4]

[0110]

According to the present invention, the tetraazaporphyrin compound according to the present invention has characteristics excellent in electrophotographic sensitivity as compared with a known pigment alone. A photoreceptor containing such a tetraazaporphyrin compound has excellent electrophotographic sensitivity.

Effect on Claim 2 The tetraazaporphyrin compound according to the present invention has characteristics excellent in electrophotographic sensitivity as compared with the case where a known pigment is used alone. Further, the laminated photoreceptor containing such a tetraazaporphyrin compound has excellent electrophotographic sensitivity.

Effect on Claim 3 The tetraazaporphyrin compound according to the present invention has characteristics excellent in electrophotographic sensitivity as compared with the case where a known pigment is used alone. Further, the laminated photoreceptor containing such a tetraazaporphyrin compound has excellent electrophotographic sensitivity.

Effect on Claim 4 The tetraazaporphyrin compound according to the present invention has characteristics excellent in electrophotographic sensitivity as compared with the case where a known pigment is used alone. Further, the single-layer photoreceptor containing the tetraazaporphyrin compound has excellent electrophotographic sensitivity.

[Brief description of the drawings]

FIG. 1 is an IR spectrum of the pigment obtained in Production Example 1.

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

Claims (4)

[Claims] An electrophotographic photoreceptor comprising a conductive support having thereon a layer containing a compound having a tetraazaporphyrin skeleton represented by the following general formula (I) as an active ingredient. 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 R ¹ , R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom , A lower alkyl group, or a substituted or undisposed aryl group.) 2. A laminated electrophotographic photoreceptor in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a hole 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 the compound represented by the general formula (I) according to 1 above. 3. A layered electrophotographic photoconductor in which a charge generation layer containing a charge generation substance and a charge transfer layer containing an electron transport substance are sequentially provided on a conductive support, wherein the charge generation layer is provided on the charge generation layer. An electrophotographic photoreceptor comprising a compound represented by the general formula (I) described above. 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. Photoreceptor.