JP2000212462A - Titanyltetraazaporphyrin derivative mixture and electrophotographic photoreceptor using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tetraazaporphyrin derivative mixture useful as an organic photoconductor used in an electrophotographic photoreceptor having excellent sensitivity and charge stability in a visible region to a near infrared region, and to use the mixture. To provide a photoconductor for electrophotography. SOLUTION: A titanyltetraazaporphyrin derivative mixture comprising various titanyltetraazaporphyrin derivatives represented by the following general formula (1), and an electrophotographic photoreceptor containing the same in a photosensitive layer. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mixture of titanyltetraazaporphyrin derivatives and an electrophotographic photoreceptor using the same, and more particularly, to a novel mixture of titanyltetraazaporphyrin derivatives and a photosensitive layer containing the mixture. The present invention relates to an electrophotographic photosensitive member.

[0002]

2. Description of the Related Art Conventionally, various inorganic and organic photoconductors are widely known as photoconductive materials of a photoconductor used in an electrophotographic system. Generally, the “electrophotographic method” here means that a photoconductive photoconductor is first placed in a dark place,
For example, it is charged by corona discharge, and then image-exposed to selectively dissipate the charge of only the exposed portion to obtain an electrostatic latent image.The latent image portion is formed from a coloring agent such as a dye or pigment and a polymer substance. This is an image forming process called a Carlson process in which an image is formed by developing with a constituent toner and visualizing the toner. Photoreceptors using organic photoconductors have advantages over inorganic photoconductors in the degree of freedom of the photosensitive wavelength range, film formability, flexibility, film transparency, mass productivity, toxicity and cost. At present, most photoconductors use organic photoconductors. The photoreceptor repeatedly used in the electrophotographic method and similar processes has excellent electrostatic characteristics such as sensitivity, receptive potential, potential holding property, potential stability, residual potential, and spectral sensitivity characteristics. Is required.

In recent years, the development of information processing systems using the electrophotographic system has been remarkable. In particular,
2. Description of the Related Art A printer using a digital recording system in which information is converted into a digital signal and information is recorded by light has been significantly improved in print quality and reliability. This digital recording method is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. Further, since a copier equipped with this digital recording technology is added with various information processing functions, its demand is expected to increase more and more in the future.

[0004] A photosensitive member compatible with such a digital recording system is required to have characteristics different from those of a conventional analog system. For example, small, inexpensive and highly reliable semiconductor lasers (LDs) and light emitting diodes (LEDs) are currently widely used as light sources. However, the emission wavelength range of the LD which is currently widely used is in the near-infrared light range, and the emission wavelength of the LED is longer than 650 nm. Therefore, in addition to the requirements for the electrophotographic photoreceptor,
It is desired to have high sensitivity from the visible light region to the near infrared light region.

From this viewpoint, squarylium dyes (JP-A-49-105536 and JP-A-58-21416), triphenylamine-based trisazo pigments (JP-A-61-151659), and phthalocyanine pigments (JP-A-61-151659) 48-34189 and 57-14874) have been proposed as photoconductors for digital recording. In particular, phthalocyanine pigments, which are titanyltetraazaporphyrin derivatives, have a photosensitive wavelength range up to a long wavelength range, have high photosensitivity, and have various variations depending on the type of central metal and crystal type. Research is being actively conducted as a photoconductor for use. Known phthalocyanine pigments exhibiting good sensitivity include ε-type copper phthalocyanine, X
Type metal-free phthalocyanine, τ type metal-free phthalocyanine,
Vanadyl phthalocyanine, titanyl phthalocyanine and the like can be mentioned.

Among these, Japanese Patent Application Laid-Open No. Sho 64-17066
JP, JP-A-3-128973, JP-A-5-9-9
No. 8182 proposes a highly sensitive titanyl phthalocyanine pigment. The spectral wavelength range of these titanyl phthalocyanine pigments shows a maximum absorption in the range of 700 to 860 nm, and shows extremely high sensitivity to semiconductor laser light. However, when the titanyl phthalocyanine pigment disclosed in each of the above publications is used for an electrophotographic photoreceptor, although the sensitivity is sufficient, practical use such as a decrease in chargeability due to repeated fatigue and a large dependence on temperature and humidity is caused. Many problems remain [Y. Fujimak
i, Proc. IS & T s 7th International
temporal Congress on Advanc
es inNon-Impact Printing
Technologies, 1,269 (1991);
K. Daimon, et al. : J. Imaging
Sci. Technol. , 40, 249 (199
6)].

[0007] In addition, Japanese Patent No. 2637487,
Japanese Patent No. 2637485 discloses a tetraazaporphyrin-based pigment having a hetero ring such as pyridine or pyrazine. Furthermore, 3-271
No. 11, Registered Patent No. 2775439 discloses that a mixture of a phthalocyanine and a pyridinoporphyrazine pigment is useful as a photoconductor. Japanese Patent Publication No. 3-27111 describes a copper phthalocyanine nitrogen isoform obtained by mixing and reacting pyridine-3,4-dicarboxylic acid and phthalic anhydride, which are raw materials of the phthalocyanine nitrogen isomorphous structure. . However, the electrophotographic photoreceptor using these materials sufficiently satisfies the requirements of the electrophotographic photoreceptor in terms of sensitivity in the visible region and near-infrared region, charging characteristics, and especially durability in repeated use. Was not.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to eliminate the above-mentioned drawbacks of the photoconductor in the conventional electrophotographic photosensitive member, and more specifically, to improve the sensitivity and chargeability in the visible to near infrared region. Excellent, and a tetraazaporphyrin derivative mixture useful as an organic photoconductor used in an electrophotographic photosensitive member having excellent electrostatic stability in repeated fatigue characteristics,
And an electrophotographic photoreceptor using the mixture.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a mixture comprising a plurality of titanyltetraazaporphyrin derivatives represented by the following general formula (1). The present invention has been completed.
That is, according to the present invention, first, there is provided a titanyltetraazaporphyrin derivative mixture comprising a plurality of titanyltetraazaporphyrin derivatives represented by the following general formula (1).

Embedded image (Where A, B, C and D are unsubstituted or as a substituent, a nitro group, a cyano group, a halogen atom, a carbon number of 1 to 8)
Represents a benzene ring or a pyridine ring which may have an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group, which may be the same or different. ) Second, in mass spectrometry, 576, 577, 578,
There is provided a mixture of the titanyltetraazaporphyrin derivatives according to the first, which has a peak at 579 and 580. Thirdly, it is composed of a plurality of titanyltetraazaporphyrin derivatives, and these titanyltetraazaporphyrin derivatives are (a) a compound of the general formula (1) wherein A, B, C, and D are all unsubstituted benzene rings; b) A, B,
A compound of the general formula (1) in which three of C and D are unsubstituted benzene rings and the other is an unsubstituted pyridine ring;
(C) a compound of the general formula (1) in which two of A, B, C and D are unsubstituted benzene rings and the other two are unsubstituted pyridine rings, (d) A, B, C and D One of which is an unsubstituted benzene ring and the other three are unsubstituted pyridine rings; and (e) a compound in which all of A, B, C, and D are unsubstituted pyridine rings. A mixture of titanyltetraazaporphyrin derivatives according to the first and second aspects, which is at least one compound of the compound of the formula (1), is provided. Fourth, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum by CuKα ray
At least 6.9 °, 26.2 °, 27.2 ° and 2 of
The titanyl tetraazaporphyrin derivative mixture according to any one of the first to third aspects, wherein the mixture exhibits a diffraction peak at one of 8.5 °. Fifthly, there is provided the titanyltetraazaporphyrin derivative mixture according to any one of the first to fourth aspects, obtained by reacting phthalonitrile, dicyanopyridine, and a titanium compound. Sixthly, there is provided a method for producing a titanyltetraazaporphyrin derivative mixture as described in the above item 1, obtained by reacting phthalonitrile, dicyanopyridine and a titanium compound. Seventh, the reaction ratio of phthalonitrile to dicyanopyridine obtained by reacting under different conditions, formed by mixing at least two kinds of titanyltetraazaporphyrin derivative mixtures according to the fifth above, A method for producing a titanyl tetraazaporphyrin derivative mixture according to the first aspect is provided. Eighthly, there is provided a method for producing the titanyl tetraazaporphyrin derivative mixture according to the first aspect, which is formed by mixing the titanyl tetraazaporphyrin derivative mixture according to the fifth aspect with a phthalocyanine-based pigment.
Ninthly, there is provided a method for producing the titanyl tetraazaporphyrin derivative mixture according to the first aspect, which is formed by subjecting the titanyl tetraazaporphyrin derivative mixture according to the fifth aspect to a crystal conversion treatment. Tenth, in an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive substrate, the photosensitive layer may contain the titanyltetraazaporphyrin derivative mixture according to any one of the first to fifth aspects. An electrophotographic photoreceptor is provided. Eleventh, there is provided an image forming apparatus including the electrophotographic photosensitive member according to the tenth aspect.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The titanyl tetraazaporphyrin derivative mixture of the present invention is a mixture comprising a plurality of titanyl tetraazaporphyrin derivatives represented by the general formula (1). The mixture provided by the present invention and comprising a plurality of titanyltetraazaporphyrin derivatives represented by the general formula (1) is a novel mixture, and can be reproduced in high yield by the production method provided by the present invention. It can be easily, stably and easily manufactured. The means for confirming and analyzing a mixture comprising a plurality of titanyltetraazaporphyrin derivatives provided by the present invention include:
For example, by performing mass spectrometry, detection can be performed by confirming the presence of a fragment peak corresponding to the value corresponding to the molecular weight of each titanyltetraazaporphyrin derivative that is a component of the mixture. Further, when a mixture of a plurality of titanyltetraazaporphyrin derivatives provided by the present invention is used for the electrophotographic photoreceptor,
It is possible to provide a highly sensitive electrophotographic photoreceptor as compared with the case where a mixture composed of a tetraazaporphyrin derivative having another central metal is used. It is considered that the use of titanyl as the central metal was effective in increasing the sensitivity. Furthermore, when a mixture of a plurality of titanyltetraazaporphyrin derivatives provided by the present invention is used for an electrophotographic photoreceptor, the electrostatic stability, especially in the repetitive fatigue characteristics, is reduced as compared with the case where a conventional titanylphthalocyanine pigment is used. In terms of being excellent. It is considered that the use as a mixture was effective for electrostatic stability in repeated fatigue characteristics. A, B, C, and D in the general formula (1) represent a benzene group or a pyridine ring which may be unsubstituted or have a substituent. Examples of the substituent include a nitro group, a cyano group, and a halogen atom. Atom or an alkyl group which may have a substituent, an alkoxy group,
And an aryl group. Specifically, as a halogen atom, iodine, bromine, chlorine, and a fluorine atom, and as an alkyl group, a methyl group, an ethyl group, an n-propyl group, an is
o-propyl, tert-butyl, sec-butyl, n-butyl, iso-butyl, trifluoromethyl, 2-cyanoethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, etc. And specific examples of the alkoxy group include a methoxy group, an ethoxy group,
n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, te
Examples thereof include an rt-butoxy group, a 2-hydroxyethoxy group, a 2-cyanoethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.
Further, as the aryl group, a phenyl group, a naphthyl group,
Biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group,
Azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group, pyridyl Group, pyridinyl group, pyrrolidyl group, oxazolyl group, and the like. These aryl groups may have the above-described alkyl group, alkoxy group, and halogen atom, and further, each of A, B, C, and D is a condensed ring. May be formed.

The tetraazaporphyrin derivative mixture represented by the general formula (1) is, for example, a mixture of a phthalonitrile represented by the following formula (2) and a dicyanopyridine represented by the following formula (3) or (4). Together with a titanium compound such as titanium tetrachloride or tetra-n-butyl orthotitanate, without solvent, or α-chloronaphthalene, dichlorobenzene, trichlorobenzene, pentanol,
It can be obtained by reacting in the presence of octanol, benzyl alcohol, N, N-dimethylformamide, N-methylpyrrolidone, quinoline, benzene, toluene, xylene, mesitylene, nitrobenzene, dioxane and the like. However, for simplicity, the compounds represented by the formulas (2), (3) and (4) are described as unsubstituted compounds as described below, but they may have the substituent. Also,
The reaction may be carried out, if necessary, with urea, formamide, acetamido, benzamide, 1,8-diazabicyclo [5,4,
0] -7-undecene (DBU), ammonia and the like. The reaction temperature is usually from room temperature to 300 ° C, preferably from 100 ° C to 250 ° C. Further, instead of the compound represented by the formula (2), the compounds represented by the formulas (5) to (7) and the compounds represented by the formulas (3) and (4) are replaced by the formulas (8) to (13) Can be used as a raw material to obtain a tetraazaporphyrin derivative mixture represented by the general formula (1) by a production method similar to the above.

[0012]

[Table 1]

In the above synthesis reaction of the tetraazaporphyrin derivative, the compound represented by the formula (2) and the compound represented by the formula (3)
Alternatively, the mixing ratio (molar ratio) with the compound represented by (4) is 1: 99999 to 99999: 1, preferably 1: 1 to 399: 1 (molar ratio). When the amount of the compound represented by the formula (2) is less than the above-mentioned mixing ratio, the chargeability and the sensitivity in the electrophotographic characteristics are lowered. Conversely, when the mixing ratio of the compound represented by the formula (3) or (4) is small, the rate of change in the decrease in charge due to static electricity, light fatigue, or the like increases.

Further, depending on the required characteristics of the photoreceptor, a mixture of two or more kinds of titanyltetraazaporphyrin derivatives having different mixing ratios or a mixture of a phthalocyanine pigment and a titanyltetraazaporphyrin derivative is also obtained.
The titanyltetraazaporphyrin derivative mixture of the present invention can be obtained. In this case, the phthalocyanine pigments include copper phthalocyanine, metal-free phthalocyanine, aluminum phthalocyanine, magnesium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, vanadyl phthalocyanine, titanyl phthalocyanine, chloroindium phthalocyanine, hydroxyindium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, and cobalt phthalocyanine. And the like.

As a photoconductor for an electrophotographic photoreceptor, the titanyltetraazaporphyrin derivative mixture of the present invention comprises:
In a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum using Cu-Kα characteristic X-ray (λ = 1.54 °), at least 6.9 °, 26.2 °, 27.2 ° or 28 It is preferably in a crystal form having a diffraction peak at 0.5 °. These crystal forms can be obtained by the above-mentioned production method. However, according to the required characteristics of the photoreceptor, a desired crystal form can be obtained by performing a crystal conversion treatment.

Examples of the method for crystal conversion of the mixture of titanyltetraazaporphyrin derivatives include acid treatment, solvent treatment, mechanical treatment, and heat treatment. Acid treatment is a process in which a pigment is dissolved in an acid such as trichloroacetic acid or trifluoroacetic acid at 0 ° C. to room temperature, and then dropped into ice, water, or an organic solvent in which a mixture of titanyltetraazaporphyrin derivatives is hardly soluble. This is a process of precipitating the crystal of the pigment and obtaining the crystal by means such as filtration. The solvent treatment is a suspension stirring treatment of the pigment in a solvent at room temperature or under heating, and the mechanical treatment is, for example, an automatic mortar, a planetary mill, a ball mill, a vibration ball mill, a kneader, an attritor. And grinding (milling) processing using a sand mill or the like.
In these milling processes, for example, glass beads,
Steel beads, alumina balls, PSZ balls, YT
It is carried out at room temperature or under heating by using a Z ball or a milling medium such as salt and sodium sulfate. The milling treatment may be performed in a system to which a solvent is added together with the milling media. The heat treatment is performed in combination with the above-described treatment method, and it is also possible to directly heat the crystal to a temperature higher than the crystal transition temperature in the air or in the presence of an inert gas using a hot plate, an electric heating furnace, or the like. Show.

Examples of the solvent used in these treatments include aromatic solvents such as benzene, toluene, dichlorobenzene and nitrobenzene, alcohol solvents such as methanol, ethanol and benzyl alcohol, acetone, cyclohexanone and methyl ethyl ketone. Ketone solvent, n-butyl ether, ethylene glycol n
Ether solvents such as -butyl ether and tetrahydrofuran; amine solvents such as N, N-dimethylformamide and N-methylpyrrolidone; basic solvents such as quinoline and pyridine; dimethyl sulfoxide; water; The titanyl tetraazaporphyrin derivative mixture of the present invention is subjected to mass spectrometry, and appears at a position corresponding to the molecular weight of each titanyl tetraazaporphyrin derivative that is a constituent component of the titanyl tetraazaporphyrin derivative mixture.
It can be confirmed by the fragment peak.

The mixture of titanyltetraazaporphyrin derivatives represented by the general formula (1) of the present invention can be used alone or in combination with a charge transporting material to produce a single-layer or laminated (separated-function) electrophotographic photosensitive member. In the case of a single-layer structure, a photosensitive layer in which a mixture of a titanyltetraazaporphyrin derivative alone or a charge transport material is dispersed in combination is provided on a conductive substrate. In the case of the function separation type, a charge generation layer composed of a mixture of titanyl tetraazaporphyrin derivatives is formed on a substrate, and a charge transport layer composed of a charge transport substance is formed thereon. May be laminated.
Further, an intermediate layer may be provided between the photosensitive layer and the substrate in order to improve adhesion and charge blocking properties. Furthermore, in order to improve mechanical durability such as friction resistance,
A protective layer may be provided on the photosensitive layer.

The photosensitive layer in which the titanyltetraazaporphyrin derivative mixture is dispersed can be provided by dissolving or dispersing a binder resin in an appropriate solvent, if necessary, coating and drying. Examples of the method of dispersing the titanyltetraazaporphyrin derivative mixture include, for example, a ball mill, an 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 photosensitive layer is formed by dispersing the mixture of titanyltetraazaporphyrin derivatives, the mixture of the titanyltetraazaporphyrin derivative is 2 μm in order to improve the dispersibility in the layer.
m 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.

The solvent used for preparing the dispersion or solution of the photosensitive layer includes, for example, N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1,1-trichlor. Examples thereof include ethane, dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, and butyl acetate.

The binder used for forming the photosensitive layer is not particularly limited, as long as it is a conventionally known binder for an electrophotographic photosensitive member having good insulating properties. Specific examples of the binder include, for example, polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin, methacrylic acid resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin , Polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone resin, melamine resin, etc., addition polymerization type resin, polyaddition type resin, polycondensation type resin, and those containing two or more of repeating units of these resins. Insulating resins such as polymer resins, for example, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and poly-N-vinyl carbazole Polymer organic semiconductors are mentioned. These binders can be used alone or
It can be used as a mixture of more than one kind.

The titanyltetraazaporphyrin derivative mixture represented by the general formula (1) used in the present invention may be used after being mixed and dispersed with, for example, the following pigments. Examples of such organic pigments include, for example,
CI Pigment Blue 25 (Color Index C
I21180), CI Pigment Red 41 (CI
21200), CI Acid Red 52 (CI45)
100), 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), azo pigments having a bisstilbene skeleton (described in JP-A-54-17733), and azo pigments 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, for example, C.I. Pigment Blue 16 (CI74100), phthalocyanine-based pigments such as titanyl phthalocyanine, and further, for example, indigo-based pigments such as C.I. Examples include perylene pigments such as Argoscarlet B (manufactured by Bayer), and Insence Scarlet R (manufactured by Bayer). These organic pigments may be used alone or in combination of two or more.

When a photoreceptor is manufactured using the above-described layer constitution and material, there are preferable ranges for the film thickness and the ratio of the material. For example, in the case of a function-separated type (lamination of a substrate / charge generation layer / charge transport layer), a binder is optionally used in the charge generation layer, and in that case, a mixture of the titanyltetraazaporphyrin derivative mixture with respect to the binder is used. 20%
The thickness is preferably from 900% to 900%, and 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 preferably 20 to 200%, and the thickness is preferably 5 to 100 μm. When a high molecular charge transport material is used, the charge transport layer may be formed alone. Further, the charge generation layer preferably contains a charge transporting substance, which has an effect on suppressing residual potential and improving sensitivity. In this case, the charge transporting material is preferably contained in an amount of 20 to 200% based on the binder.
In the case of a single-layer type photoreceptor, the ratio of the titanyltetraazaporphyrin derivative mixture to the binder resin in the photosensitive layer is preferably 5 to 95%, and the film thickness is preferably 10 to 100 μm. When combined with a charge transport material, the ratio of the charge transport material to the binder resin is 30 to 2
00% is preferred. In addition, the photosensitive layer may be formed of a mixture of a polymer-type charge transport material and a titanyltetraazaporphyrin derivative. In this case, the ratio of the mixture of the titanyltetraazaporphyrin derivative to the polymer-type charge transport material is 5 to 95%, The thickness is preferably set to 10 to 100 μm.

Further, in the photosensitive layer, a phenol compound, a hydroquinone compound,
Hindered phenol compounds, hindered amine compounds, compounds in which hindered amine and hindered phenol are present in the same molecule, and the like 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 intermediate layer is provided on the conductive substrate. The intermediate layer generally contains a resin as a main component.
Considering that the photosensitive layer is coated thereon with a solvent, these resins are preferably resins having high solvent resistance to general organic solvents. Examples of such a resin include water-soluble resins such as polyvinyl alcohol, casein and sodium polyacrylate, alcohol-soluble resins such as copolymerized nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy resin. Curable resins that form a three-dimensional network structure, such as resins, are exemplified. In order to prevent moire and reduce residual potential, a fine powder pigment of a metal oxide exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the intermediate layer. These intermediate layers can be formed using an appropriate solvent and a coating method as in the above-described photosensitive layer. Further, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the intermediate layer of the present invention.
In addition, the intermediate layer according to the present invention is provided with Al ₂ O ₃ by anodization, an organic substance such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO _2.
Inorganic substances such as those provided by a vacuum thin film forming method can also be used. In addition, known materials can be used. The thickness of the intermediate layer is suitably from 0 to 5 μm.

Further, in the present invention, a protective layer is provided on the photosensitive layer if necessary. Examples of materials used for the protective layer include ABS resin, ACS resin and olefin resin.
Vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide,
Polyamide imide, polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS
Resin, butadiene-styrene copolymer, polyurethane,
Resins such as polyvinyl chloride, polyvinylidene chloride, and epoxy resin are exemplified. For the purpose of improving abrasion resistance, the protective layer is made of a fluororesin such as polytetrafluoroethylene, a silicone resin, or an inorganic material such as titanium oxide, tin oxide or potassium titanate dispersed in these resins. Etc. can be added. As a method for forming the protective layer, a normal coating method is employed. The thickness of the protective layer is suitably about 0.1 to 10 μm. In addition to the above, a-C, a-Si formed by a vacuum thin film forming method
A known material such as C can be used as the protective layer.

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) Compounds represented by the following formula (21) (JP-A-55-154955, JP-A-55-1569)
No. 54)

Embedded image (Wherein, R ¹ represents a methyl group, an ethyl group, 2-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 alkoxyl group having 1 to 4 carbon atoms, a dialkylamino group or a nitro group. )

The compound represented by the general formula (21) includes, for example, 9-ethylcarbazole-3-aldehyde-1-aldehyde.
Methyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-1-benzyl-1-phenylhydrazone, 9-ethylcarbazole-3-aldehyde-
Examples include 1,1-diphenylhydrazone.

(2) Compound represented by the following formula (22) (described in JP-A-55-52063)

Embedded image (In the formula, Ar represents a naphthalene ring, an anthracene ring, a styryl ring, a substituted product thereof, a pyridine ring, a furan ring, or a thiophene ring, and R represents an alkyl group or a benzyl group.)

The compound represented by the general formula (22) includes, for example, 4-diethylaminostyryl-3-aldehyde-
There are 1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-aldehyde-1-benzyl-1-phenylhydrazone and the like.

(3) Compound represented by the following formula (23) (described in JP-A-56-81850)

Embedded image (Wherein, R ¹ represents an alkyl group, a benzyl group, a phenyl group or a naphthyl group; R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, Represents an aralkylamino group or a diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R ² may be the same or different. R ³ represents a hydrogen atom or a methoxy group.)

The compound represented by the general formula (23) includes, for example, 4-methoxybenzaldehyde-1-methyl-1
-Phenylhydrazone, 2,4-dimethoxybenzaldavido-1-benzyl-1-phenylhydrazone, 4-
Diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1-benzyl-1- (4-methoxy) phenylhydrazone, 4-
Diphenylaminobenzaldehyde-1-benzyl-1
-Phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone and the like.

(4) Compound represented by the following formula (24) (described in JP-A-51-10983)

Embedded image (Wherein, R ¹ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R ² , R ³
May be the same or different and each represents a hydrogen atom, 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 are bonded to each other And may form a heterocycle containing nitrogen. 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. )

The compound represented by the general formula (24) includes, for example, 1,1-bis (4-dibenzylaminophenyl)
Examples include propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-dibenzylaminophenyl) propane, and 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane.

(5) Compound represented by the following formula (25) (described in JP-A-51-94829)

Embedded image (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.)

Examples of the compound represented by the general formula (25) include 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene.

(6) Compound represented by the following formula (26) (described in JP-A-52-128373)

Embedded image [In the formula, R ¹ represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, and Ar represents

Embedded image R ² represents an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
Represents an alkoxy group or a dialkylamino group having 1 to 4 carbon atoms, n is 1 or 2, when n is 2, R ³ may be the same or different, and R ⁴ and R ⁵ are a hydrogen atom, a carbon atom Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted benzyl group represented by Formulas 1 to 4. ]

As the compound represented by the general formula (26), for example, 9- (4-dimethylaminobenzylidene)
Fluorene, 3- (9-fluorenylidene) -9-ethylcarbazole and the like.

(7) Compound represented by the following general formula (27) (described in JP-A-56-29245)

Embedded image (Wherein R is a carbazolyl group, a pyridine 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, and these substituents are a dialkylamino group,
Alkyl group, alkoxy group, carboxy group or ester thereof, halogen atom, cyano group, aralkylamino group,
Represents a group selected from the group consisting of N-alkyl-N-aralkylamino, amino, nitro and acetylamino. )

The compound represented by the general formula (27) includes, for example, 1,2-bis (4-diethylaminostyryl) benzene, 1,2-bis (2,4-dimethoxystyryl)
There is benzene.

(8) Compound represented by the following general formula (28) (described in JP-A-58-58552)

Embedded image (Wherein, R ¹ represents a lower alkyl group, a substituted or unsubstituted phenyl group or a benzyl group, and R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, an amino group or Represents an amino group substituted by a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2.)

The compound represented by the general formula (28) includes, for example, 3-styryl-9-ethylcarbazole,
(4-methoxystyryl) -9-ethylcarbazole and the like.

(9) Compound represented by the following formula (29) (described in JP-A-57-73075)

Embedded image (Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ² and R ³ represents an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, R ⁴ Represents a hydrogen atom or a substituted or unsubstituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group or a naphthyl group.)

The compound represented by the general formula (29) includes, for example, 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene,
1- (4-diphenylaminostyryl) naphthalene, 1
-(4-diethylaminostyryl) naphthalene and the like.

(10) Compound represented by the following formula (30) (described in JP-A-58-198043)

Embedded image [Wherein, n is an integer of 0 or 1, R ¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group;
¹ represents a substituted or unsubstituted aryl group, R ⁵ represents an alkyl group containing a substituted alkyl group or a substituted or unsubstituted aryl group, A represents a 9-anthryl group, a substituted or unsubstituted carbazolyl group or

Embedded image Wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or

Embedded image (However, R ³ and R ⁴ represent an alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group, and R ³ and R ⁴ may be the same or different, and form a ring. M is an integer of 0, 1, 2 or 3, and 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. ]

The compound represented by the general formula (30) includes, for example, 4'-diphenylamino-α-phenylstilbene, 4'-bis (methylphenyl) amino-α-phenylstilbene and the like.

(11) Compound represented by the following formula (31) (described in JP-A-49-105537)

Embedded image (In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a dialkylamino group or a halogen atom, and n represents 0 or 1.)

Compounds represented by the general formula (31) include, for example, 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazolin, 1-phenyl-3- (4- Dimethylaminostyryl) -5- (4-dimethylaminophenyl) pyrazolin.

(12) Compound represented by the following formula (32) (described in JP-A-52-139066)

Embedded image (In the formula, 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.)

The compound represented by the general formula (32) 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.

(13) A compound represented by the following general formula (33) (described in JP-A-52-139065)

Embedded image (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 group. Represents an aryl group.)

As the compound represented by the general formula (33), for example, 2-N, N-diphenylamino-5- (N
-Ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- (4-diethylaminophenyl)-
5- (N-ethylcarbazol-3-yl) -1,3,3
4-oxadiazole and the like.

(14) Compound represented by the following formula (34) (described in JP-A-58-32372)

Embedded image (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 ,
R ³ may be the same or different and represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. )

The benzidine compound represented by the general formula (34) 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.

(15) Compound represented by the following general formula (35) (described in JP-A-2-178669)

Embedded image (Wherein R ¹ , R ³ and R ⁴ are a hydrogen atom, 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 Is an aryl group of R
² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group, or a halogen atom. Where R ¹ , R ² ,
R ³ and R ⁴ exclude the case where all are hydrogen atoms. Also,
k, l, m and n are integers of ¹ , ² , 3 or 4, and 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. Is also good. )

The biphenylamine compound represented by the general formula (35) 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.

(16) Compound represented by the following formula (36) (described in JP-A-3-285960)

Embedded image (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, an alkoxy group,
Represents a substituted or unsubstituted phenyl group, which may be the same or different. )

Examples of the triarylamine compound represented by the general formula (36) include 1-diphenylaminopyrene and 1-di (p-tolylamino) pyrene.

(17) Compound represented by the following formula (37) (described in JP-A-62-98394)

A-CH = CH-Ar-CH = CH-A (37) wherein Ar represents a substituted or unsubstituted aromatic hydrocarbon group;

Embedded image (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). ]

The diolefin aromatic compound represented by the general formula (37) includes, for example, 1,4-bis (4-diphenylaminostyryl) benzene, 1,4-bis [4-di (p-tolyl) [Aminostyryl] benzene.

(18) A compound represented by the following general formula (38) (described in JP-A-4-230766)

Embedded image (In the formula, Ar represents an aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, n is 0 or 1, and m is 1
Or 2, when n = 0 and m = 1, Ar and R may form a ring together. )

Examples of the styrylpyrene compound represented by the general formula (38) include 1- (4-diphenylaminostyryl) pyrene and 1- [4-di (p-tolyl) aminostyryl] pyrene.

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] thiophen-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide and the like.
The electron transporting substances listed in the formulas (9), (40) and (41) can be suitably used. These charge transport materials are used alone or in combination of two or more.

[0066]

Embedded image

Embedded image

Embedded image

The titanyltetraazaporphyrin derivative mixture represented by the general formula (1) of the present invention is useful not only as a photoconductor of an electrophotographic photoreceptor but also in the field of electronics such as solar cells and optical disks. It can be suitably used as a device.

[0068]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 19.48 g (152.0 mmol) of phthalonitrile,
1.03 g (8.00 mmol) of 2,3-dicyanopyridine
l), 14.97 g of tetra-n-butyl orthotitanate
(44.00 mmol), 4.80 g (80.00) of urea.
mmol) and 24.48 g of 1-octanol were heated and stirred at 150 to 161 ° C. for 6 hours in a nitrogen stream.
After cooling, 80 ml of methanol was added, and the mixture was stirred under reflux for 30 minutes and cooled to room temperature. The crystals obtained by filtration were washed with toluene, methanol and water, dried under reduced pressure, heated and dried to give a titanyl tetra powder of blue powder. 19.38 g (yield: 84.0%) of an azaporphyrin derivative mixture (Compound No. 1) was obtained. The results of elemental analysis were as follows. C H N measured value (%) 66.74 2.64 19.45 Next, in order to examine the reproducibility of the method for producing a titanyltetraazaporphyrin derivative mixture provided by the present invention, the same contents as described above were used. According to the production method, a mixture of titanyl tetraazaporphyrin derivatives (compound N
o. Production of 1) was performed 10 times. Elemental analysis of the obtained titanyl tetraazaporphyrin derivative mixture showed that the difference between the actually measured values of C, H, and N was within 3%. Therefore, the titanyl tetraazaporphyrin derivative mixture was produced by the production method described in the present invention. Was confirmed to be able to be produced with good reproducibility.

The powder X-ray diffraction spectrum of the obtained mixture of titanyltetraazaporphyrin derivatives was measured under the following conditions. FIG. 1 shows a powder X-ray diffraction spectrum of the obtained titanyltetraazaporphyrin derivative mixture. The strongest diffraction peak was shown at a Bragg angle (2θ) of 26.2 °. X-ray tube Cu (wavelength 1.54 °) Voltage 50 kV Current 30 mA Scanning speed 2 deg / min Scanning range 3 to 40 deg Time constant 2 sec Next, mass spectrometry of the obtained titanyl tetraazaporphyrin derivative mixture is performed under the following measurement conditions. I went in. LC / MS equipment Manufacturer: JEOL Model name: Mass spectrometer Model number: MS700 Measurement conditions Ionization: ESI method Positive ion detection Sample introduction flow rate: 25 μL / min Sample introduction method: Infusion method Ring voltage: 80 V Skimmer voltage : 0 V Sample preparation The sample was dissolved in formic acid, and further diluted with a 50% formic acid aqueous solution to adjust the concentration to 50 ppm. FIG. 1 shows the results of mass spectrometry of the obtained mixture of titanyltetraazaporphyrin derivatives.
0 is shown. The titanyltetraazaporphyrin derivative mixture is composed of components having the following five molecular weights. -Component 1 In the general formula (1), the molecular weight when all of A, B, C, and D are unsubstituted benzene rings: 576-Component 2 In the general formula (1), A, B, and C are free. Molecular weight when substituted benzene ring and D is an unsubstituted pyridine ring: 577 ・ Component 3 In the general formula (1), two of A, B, C and D are unsubstituted benzene rings. , Molecular weight when the other two are unsubstituted pyridine rings: 578 ・ Component 4 In the general formula (1), A is an unsubstituted benzene ring, and B, C, and D are unsubstituted pyridine rings. Molecular weight in a certain case: 579 ・ Component 5 In the general formula (1), molecular weight in a case where A, B, C, and D are all unsubstituted pyridine rings: 580 In the mass spectrometry results in FIG. 576, 577, corresponding to a molecular weight of 5. 578, 579, 58
A peak was detected at 0.

Examples 2 to 7 The same procedure as in Example 1 was carried out except that the mixing ratio of phthalonitrile and 2,3-dicyanopyridine was changed, to obtain a mixture of titanyltetraazaporphyrin derivatives (compounds Nos. 2 to 2).
7) was manufactured. Table 2 shows these yields, and Table 3 shows the Bragg angle (2θ) of the strongest diffraction peak in the powder X-ray diffraction spectrum as a result of elemental analysis.

[0072]

[Table 2]

[0073]

[Table 3]

Example 8 80 g of concentrated sulfuric acid was stirred and cooled in an ice-water bath, and 5.00 g of the titanyltetraazaporphyrin derivative mixture (Compound No. 1) obtained in Example 1 was added little by little over 30 minutes to dissolve. I let it. After stirring for 1 hour, the content was dropped into 500 g of ice water, and after stirring for 30 minutes, filtration was performed. The obtained crystals are washed three times with water and filtered to obtain a wet cake.
9 g was obtained (solid content concentration: 17.3%). FIG. 2 shows a powder X-ray diffraction diagram of the titanyltetraazaporphyrin derivative mixture obtained by drying this under reduced pressure and pressure. 9.7 g of ion-exchanged water and 120 g of tetrahydrofuran were added to 17.3 g of the wet cake, and the mixture was stirred at room temperature for 6 hours.
This was filtered, dried under reduced pressure, and a blue crystal of a titanyltetraazaporphyrin derivative mixture (Compound No.
8) 2.72 g were obtained. FIG. 3 shows a powder X-ray diffraction spectrum of this titanyltetraazaporphyrin derivative mixture.
The strongest diffraction peak was shown at a Bragg angle (2θ) of 27.2 °. As a result of elemental analysis, the Bragg angle (2θ) of the strongest diffraction peak in the powder X-ray diffraction spectrum
Are shown in Table 4.

Examples 9 to 14 Compound Nos. Compound No. 1 Except for 2-7,
By operating in the same manner as in Example 8, a mixture of titanyltetraazaporphyrin derivatives (Compound Nos. 9 to 14) was obtained. Table 4 shows the elemental analysis results of the obtained titanyltetraazaporphyrin derivative mixture and the Bragg angle (2θ) of the strongest diffraction peak in the powder X-ray diffraction spectrum.

[0076]

[Table 4]

To the 1.00 g of the crystal obtained by heating and drying the wet cake in Example 8 under reduced pressure, 50 ml of tetrahydrofuran was added, and the mixture was stirred under reflux for 6 hours. The mixture was cooled to room temperature, and the residue obtained by filtration was dried by heating under reduced pressure to give a blue powdered titanyltetraazaporphyrin derivative mixture (compound N).
o. 15) 0.97 g was obtained. FIG. 4 shows a powder X-ray diffraction pattern of this product. Table 5 shows the elemental analysis results of the obtained titanyltetraazaporphyrin derivative mixture and the Bragg angle (2θ) of the strongest diffraction peak in the powder X-ray diffraction spectrum.

Examples 16 to 18 Compound Nos. Compound No. 1 A titanyltetraazaporphyrin derivative mixture (Compound Nos. 16 to 18) was obtained in the same manner as in Example 15, except that the composition was changed to 2, 3, and 6. Table 5 shows the elemental analysis results of the obtained titanyltetraazaporphyrin derivative mixture and the Bragg angle (2θ) of the strongest diffraction peak in the powder X-ray diffraction spectrum. FIG. 16 shows a powder X-ray diffraction spectrum diagram of No. 16.

[0079]

[Table 5]

Example 19 30 g of concentrated sulfuric acid was stirred and cooled in an ice-water bath, and 0.191 g (0.33 mmol) of the titanyltetraazaporphyrin derivative mixture (Compound No. 7) obtained in Example 7 was added thereto.
And 1.71 g of titanyl phthalocyanine (0.33 × 9 m
mol) was added little by little over 30 minutes to dissolve. After stirring for 1.5 hours, the content is 190 g
, And the mixture was stirred for 30 minutes, filtered, and washed with water to obtain 12.7 g of a wet cake. This wet cake 6.7
3.3 g of ion-exchanged water and 40 g of tetrahydrofuran
Was added, and the mixture was stirred at room temperature for 6 hours. This was filtered and dried under reduced pressure to obtain a titanyltetraazaporphyrin derivative mixture of blue crystals (compound No. 19).
94 g were obtained. FIG. 6 shows a powder X-ray diffraction spectrum of the obtained titanyltetraazaporphyrin derivative mixture. The strongest diffraction peak was shown at a Bragg angle (2θ) of 27.2 °.

Example 20 A mixture having the following composition was placed in a ball mill pot, and
Using an alumina ball of m, ball milling was performed for 48 hours to prepare a coating solution for the intermediate layer. Oil-free alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckolite M640)
1) 1.5 parts, melamine resin (manufactured by Dainippon Ink and Chemicals, Inc .:
1 part of Super Beckamine G-821), 5 parts of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd .: Taipaque CR-EL) and 22.5 parts of 2-butanone. This coating solution was applied on an aluminum plate support and dried at 130 ° C. for 20 minutes to form an intermediate layer having a thickness of about 4 μm. Next, a dispersion composed of 3 parts of titanyl tetraazaporphyrin derivative (Compound No. 1), 2 parts of polyvinyl butyral resin (BM-S, manufactured by Sekisui Chemical Co., Ltd.), and 495 parts of tetrahydrofuran was placed in a ball mill pot, and a PSZ having a diameter of 2 mm was taken. Using a ball, ball milling was performed for 3 hours to prepare a charge generation layer coating solution. This coating solution was applied on the intermediate layer and dried at 100 ° C. for 20 minutes to form a charge generating layer having a thickness of about 0.3 μm.

Subsequently, 7 parts of a charge transport material represented by the following general formula (42) and a polycarbonate resin (manufactured by Teijin Chemicals Ltd .:
PCX-5) 10 parts, dichloromethane 83 parts, silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF-50) 0.0002 part to prepare a charge transport layer coating solution, and after coating on the charge generation layer, at 110 ° C. for 20 minutes. After drying, a charge transport layer having a thickness of about 28 μm was formed, and an electrophotographic photosensitive member was produced.

[0083]

Embedded image

The electrophotographic photosensitive member obtained as described above
EPA-8100 (made by Kawaguchi Electric Works)
Used, dynamic method (rotation speed 1000rpm)
Measured. First, it is charged at an applied voltage of -6 KV for 20 seconds.
After that, the surface potential Vo (V) when attenuated for 20 seconds is measured.
Surface light from a halogen lamp
Exposure was performed so as to be 5.3 lux. Feeling
The surface potential at the time of exposure is from -800 (V) to -400.
The time required until (V) is obtained, and the half-life exposure amount Ew1 / 2
(Lux · sec) was calculated. In addition, 7
The illuminance on the photoreceptor surface is 1 μW / cm when monochromatic light of 80 nm is irradiated.
^TwoAnd the surface potential of the photoconductor is -800.
Half-exposure amount Em1 / 2 required from V to -400V
(ΜJ / cm ^Two) With the sensitivity in the LD light source region (near infrared region)
And measured. Table 6 shows Vo, Ew1 / 2 and Em1 / 2.
Show. In Example 1, the titanium provided by the present invention
Method for producing a mixture of nyltetraazaporphyrin derivatives
Titanil tet manufactured to study reproducibility
Laazaporphyrin derivative mixture (Compound No. 1) 1
An electrophotographic photoreceptor is similarly prepared for the zero point,
When the performance was evaluated, the electrophotographic characteristics
The actuality was good.

Examples 21 to 38 The same procedures as in Example 20 were carried out to obtain Compound Nos. The characteristics of the electrophotographic photosensitive members of Nos. 2 to 19 were evaluated. Table 6 shows the results.

Example 39 Example 20 on an aluminum evaporated polyester film
Coating the charge transport layer coating solution used in
For 10 minutes to form a charge transport layer having a thickness of about 20 μm. 13.5 parts of a titanyltetraazaporphyrin derivative mixture (Compound No. 15) obtained in Example 15,
5.4 parts of polyvinyl butyral resin (manufactured by Union Carbide Plastics Co., Ltd .: XYHL), 680 parts of tetrahydrofuran and 1020 parts of ethyl cellosolve were pulverized and mixed in a ball mill, and 1700 parts of ethyl cellosolve was added and mixed, and then the mixture was coated with a charge generating layer. A liquid was made. This coating solution is spray-coated on the charge transport layer,
For 10 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 (manufactured by Toray Industries, Inc .: CM-8000) 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. The photosensitive member was formed.
This photoconductor was evaluated in the same manner as in Example 20, except that the applied voltage was changed to +6 KV. Table 6 shows the results.

Example 40 To 1 part of the titanyltetraazaporphyrin derivative mixture (Compound No. 12) obtained in Example 12 was added 158 parts of methyl ethyl ketone, and ball milling was carried out for 24 hours using a φ5 mm alumina ball. The following equation (3)
12) an electron transporting material represented by 9), a polyester resin (manufactured by DuPont: Polyester Adhesive 4900)
0) 18 parts were added, and the dispersion obtained by further mixing was applied on an aluminum-evaporated polyester film using a doctor blade, and dried at 100 ° C. for 30 minutes to form a photosensitive layer having a thickness of about 15 μm. A photoreceptor was made. This photoconductor was evaluated in the same manner as in Example 20, except that the applied voltage was changed to +6 KV. The results are shown in Table 6.

[0088]

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Comparative Example 1 The phthalonitrile in Example 1 was replaced with the same mole of 2,2.
Titanyltetrapyridotetraazaporphyrin represented by the following general formula (43) was obtained under the same production conditions as in Example 1 except that 3-dicyanopyridine was used (Comparative Compound No. 1). Comparative compound no. FIG. 11 shows the results of mass spectrometry of Example 1 performed under the same conditions as in Example 1. Comparative compound no. A fragment peak was detected at 580, corresponding to a molecular weight of 1, indicating a single component. Further, instead of the titanyl tetraazaporphyrin derivative mixture (compound No. 1) used in Example 20,
This comparative compound No. Example 2 except that No. 1 was used.
A photoreceptor was prepared and evaluated in the same manner as in Example 1. Table 6 shows the results.

[0090]

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Comparative Example 2 55 g of concentrated sulfuric acid was stirred and cooled in an ice water bath, and 0.174 g (0.3 mmol) of titanyltetrapyridotetraazaporphyrin (Comparative Compound No. 1) obtained in Comparative Example 1 was added thereto.
l) and 3.29 g of titanyl phthalocyanine (0.3 × 1
9 mmol) was added little by little over 30 minutes to dissolve. After stirring for 1.5 hours, the contents are brought to 350
g of ice water, stirred for 30 minutes and filtered.
After washing with water, 24.0 g of a wet cake was obtained. 5. This wet cake
3.07 g of ion-exchanged water and 40 g of tetrahydrofuran were added to 93 g, and the mixture was stirred at room temperature for 6 hours. This was filtered, dried under reduced pressure, and mixed with a titanyltetraazaporphyrin derivative mixture of blue crystals (Comparative Compound No.
2) 0.96 g was obtained. Further, a mixture of the titanyltetraazaporphyrin derivatives (compound N) used in Example 20
o. Instead of this comparative compound No. 1) A photosensitive member was prepared and evaluated in the same manner as in Example 20, except that Sample No. 2 was used. Table 6 shows the results. From Table 6, it can be seen that the photoreceptor using the titanyltetraazaporphyrin derivative mixture of the present invention is considerably superior in the charging potential Vo and the sensitivities Ew1 / 2 and Em1 / 2 as compared with the photoreceptors of Comparative Examples 1 and 2. I understand.

Comparative Example 3 The procedure of Example 20 was repeated, except that the titanyltetraazaporphyrin derivative mixture (Compound No. 1) used in Example 20 was replaced with a Y-type titanyl phthalocyanine having a powder X-ray diffraction spectrum shown in FIG. A photoconductor was prepared in the same manner as in Example 20. The electrostatic fatigue characteristic of the electrophotographic photosensitive member is expressed by E
The measurement was performed using a PA-8100 (manufactured by Kawaguchi Electric Works) using a dynamic method (rotational speed: 1000 rpm). The photosensitive member is charged at an applied voltage of about -6 KV, and white light exposure with a halogen lamp is repeated, and a passing current of about 5.6 .mu.
A, 60 minutes (30 minutes + 30 minutes) while maintaining the charging potential at -800 (V). Example 20
The electrostatic fatigue characteristics of the photoreceptor obtained under the above conditions were measured under the same conditions. FIG. 8 shows these changes in the surface potential Vo (V). 8 shows that the photosensitive member of Example 20 of the present invention is comparative example 3
It can be seen that the stability of the electrostatic potential in the repetitive fatigue characteristics is superior to that of the photosensitive member of No. It is considered that the use of a mixture of a plurality of titanyltetraazaporphyrin derivatives was effective for electrostatic stability in repeated fatigue characteristics. Comparative Example 4 The following copper tetraazaporphyrin derivative mixture (Comparative Compound No. 3) was produced and evaluated according to the method of Example 16 described in JP-B-3-27111. 0.84 g of pyridine-3,4-dicarboxylic acid (5.0 mmol
l), 14.07 g of phthalic anhydride (95.0 mmol)
l), urea 24.02 g (400 mmol), cuprous chloride 2.48 g (25 mmol), ammonium molybdate tetrahydrate 0.04 g and trichlorobenzene 80 g
Was heated and stirred at 181 to 182 ° C. for 15 hours in a nitrogen stream. After cooling, 80 ml of methanol was added, and the mixture was refluxed and stirred for 30 minutes and cooled to room temperature. The crystals obtained by filtration were washed successively with toluene, methanol, a 3% aqueous sodium hydroxide solution, water, 1% hydrochloric acid and water. After, 100 ℃
Under reduced pressure for 2 days. 11. The obtained blue powder is washed with dioxane for 2 days using a Soxhlet extractor, dried by heating under reduced pressure at 100 ° C. for 2 days, and mixed with a copper tetraazaporphyrin derivative of blue powder (Comparative Compound No. 3). 51 g were obtained. FIG. 9 shows a powder X-ray diffraction spectrum of the obtained copper tetraazaporphyrin derivative mixture. Further, a mixture of the titanyltetraazaporphyrin derivatives (compound N) used in Example 20
o. In place of this comparative compound No. 1) A photosensitive member was prepared and evaluated in the same manner as in Example 20, except that Sample No. 3 was used. Table 6 shows the results. When the copper tetraazaporphyrin derivative mixture was used for the electrophotographic photoreceptor, no photosensitivity was observed for white light and monochromatic light.

[Table 6]

[0093]

[Table 7]

From Table 7, it can be seen that the electrophotographic photoreceptors of the examples have excellent chargeability and excellent sensitivity in the visible to near infrared region. Example 41 When an image was formed using an image forming apparatus equipped with the electrophotographic photosensitive member prepared in Example 20, a clear image was obtained.

[0095]

As is clear from the above description, the mixture of titanyltetraazaporphyrin derivatives of the present invention is useful as an organic photoconductor used for an electrophotographic photosensitive member for a high-speed copying machine or a laser printer. . Also,
The electrophotographic photoreceptor using the titanyltetraazaporphyrin derivative mixture of the present invention is superior in sensitivity, chargeability in the visible to near-infrared region, and repeated fatigue as compared with conventionally known titanyltetraazaporphyrin derivatives. It has excellent durability in characteristics and is useful as a photoreceptor for high-speed copying machines, laser printers and the like.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction spectrum of a mixture of titanyltetraazaporphyrin derivatives obtained in Example 1.

FIG. 2 is a powder X-ray diffraction spectrum of the titanyltetraazaporphyrin derivative mixture obtained in Example 8.

FIG. 3 is a powder X-ray diffraction spectrum of the titanyltetraazaporphyrin derivative mixture obtained in Example 8.

FIG. 4 is a powder X-ray diffraction spectrum of the titanyltetraazaporphyrin derivative mixture obtained in Example 15.

FIG. 5 is a powder X-ray diffraction spectrum of the mixture of titanyltetraazaporphyrin derivatives obtained in Example 16.

FIG. 6 is a powder X-ray diffraction spectrum of the titanyltetraazaporphyrin derivative mixture obtained in Example 19.

FIG. 7 is a powder X-ray diffraction spectrum of the Y-type titanyl phthalocyanine used in Comparative Example 3.

FIG. 8 is a diagram showing a change in surface potential in measurement of electrostatic fatigue characteristics of the electrophotographic photosensitive members obtained in Example 20 and Comparative Example 3.

FIG. 9 is a powder X-ray diffraction spectrum of the copper tetraphthalocyanine used in Comparative Example 4.

FIG. 10 is a diagram showing a result of mass spectrometry of the titanyltetraazaporphyrin derivative mixture obtained in Example 1.

11 is a diagram showing the results of mass spectrometry of titanyltetrapyridotetraazaporphyrin (Comparative Compound No. 1) obtained in Comparative Example 1. FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/06 371 G03G 5/06 371 // C07D 487/22 C07D 487/22 C07F 7/28 C07F 7 / 28F (72) Inventor Kaoru Tadokoro 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Chiaki 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72 Inventor Michihiko Nanba 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (11)

[Claims] 1. A titanyltetraazaporphyrin derivative mixture comprising a plurality of titanyltetraazaporphyrin derivatives represented by the following general formula (1). Embedded image (Where A, B, C and D are unsubstituted or as a substituent, a nitro group, a cyano group, a halogen atom, a carbon number of 1 to 8)
Represents a benzene ring or a pyridine ring which may have an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group, which may be the same or different. ) 2. In a mass spectrometer, 576, 577, 5
2. The mixture of titanyl tetraazaporphyrin derivatives according to claim 1, which has a peak at 78, 579, 580. 3. The titanyltetraazaporphyrin derivative comprising a plurality of titanyltetraazaporphyrin derivatives, wherein the titanyltetraazaporphyrin derivative is at least one compound selected from the following (a) to (e): Porphyrin derivative mixture. (A) A compound of the general formula (1) in which A, B, C and D are all unsubstituted benzene rings. (B) A compound of the general formula (1) in which three of A, B, C and D are unsubstituted benzene rings and the other is an unsubstituted pyridine ring. (C) A compound of the general formula (1) wherein two of A, B, C and D are unsubstituted benzene rings and the other two are unsubstituted pyridine rings. (D) A compound of the general formula (1) in which one of A, B, C and D is an unsubstituted benzene ring and the other three are unsubstituted pyridine rings. (E) A compound of the general formula (1) wherein A, B, C and D are all unsubstituted pyridine rings. 4. A Bragg angle (2θ ± 0.2 °) of at least 6. in an X-ray diffraction spectrum by CuKα ray.
The titanyl tetraazaporphyrin derivative mixture according to any one of claims 1 to 3, which shows a diffraction peak at one of 9 °, 26.2 °, 27.2 °, and 28.5 °. 5. The titanyltetraazaporphyrin derivative mixture according to claim 1, which is obtained by reacting phthalonitrile, dicyanopyridine, and a titanium compound. 6. The method for producing a titanyl tetraazaporphyrin derivative mixture according to claim 1, which is obtained by reacting phthalonitrile, dicyanopyridine, and a titanium compound. 7. A reaction product obtained by reacting phthalonitrile to dicyanopyridine under different reaction ratios,
The method for producing a titanyl tetraazaporphyrin derivative mixture according to claim 1, which is formed by mixing at least two kinds of the titanyl tetraazaporphyrin derivative mixtures according to claim 5. 8. The method for producing a titanyl tetraazaporphyrin derivative mixture according to claim 1, which is formed by mixing the titanyl tetraazaporphyrin derivative mixture according to claim 5 with a phthalocyanine-based pigment. 9. The method for producing a titanyl tetraazaporphyrin derivative mixture according to claim 1, which is formed by subjecting the titanyl tetraazaporphyrin derivative mixture according to claim 5 to a crystal conversion treatment. 10. An electrophotographic photoreceptor comprising at least a photosensitive layer provided on a conductive substrate, wherein the photosensitive layer contains the titanyltetraazaporphyrin derivative mixture according to any one of claims 1 to 5. An electrophotographic photosensitive member characterized by the following. 11. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 10.