JP2563810B2 - Photoconductor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor, for example, a photoconductor for electrophotography, and more particularly to a photoconductor which is used in a printer, a copying machine or the like and has high sensitivity to light having a wavelength longer than visible light and semiconductor laser light. Is.

B. 2. Description of the Related Art Conventionally, electrophotographic photoconductors having photosensitivity to visible light have been widely used in copying machines, printers and the like. As such an electrophotographic photoreceptor, an inorganic photoreceptor having a photosensitive layer containing an inorganic photoconductive substance such as selenium, zinc oxide, or cadmium sulfide as a main component is widely used. However, such an inorganic photoreceptor is not always satisfactory in the characteristics such as photosensitivity, thermal stability, moisture resistance and durability required for an electrophotographic photoreceptor of a copying machine or the like. For example, selenium crystallizes due to heat, stains on fingerprints when touched by hand, and the like, so that the above-described characteristics of the electrophotographic photosensitive member are likely to deteriorate. Further, the electrophotographic photoreceptor using cadmium sulfide is inferior in moisture resistance and durability, and the electrophotographic photoreceptor using zinc oxide has a problem in durability. In addition, the electrophotographic photoreceptor of selenium and cadmium sulfide has a drawback that there are great restrictions in terms of production and handling.

In order to improve such problems of inorganic photoconductive substances, it has been attempted to use various organic photoconductive substances in the photosensitive layer of an electrophotographic photoreceptor, and research and development have been actively conducted in recent years. Has been. For example, Japanese Patent Publication No. 10496/1975 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-trinitro-9-fluorenone. However, this photoreceptor is also insufficient in sensitivity and durability. Therefore, a function-separated electrophotographic photoreceptor has been developed in which the photosensitive layer is divided into two layers, the carrier generating layer and the carrier transporting layer are separately formed, and the carrier generating substance and the carrier transporting substance are respectively contained therein.
This is because the carrier generating function and the carrier transporting function can be individually assigned to different substances, and a substance exhibiting each function can be selected from a wide range. The body is relatively easy to obtain. Therefore, it is expected that an organic photoreceptor having high sensitivity and high durability can be obtained.

As a carrier generating substance effective for the carrier generating layer of such a function-separated type electrophotographic photosensitive member, many substances have been proposed in the past. Examples of using inorganic substances include:
Examples thereof include amorphous selenium as described in JP-B-43-16198. This carrier generation layer containing amorphous selenium is used in combination with the carrier transport layer containing an organic carrier transport substance. However, there is a problem that the carrier generation layer made of amorphous selenium is crystallized by heat or the like as described above and its characteristics are deteriorated. Examples of using an organic substance as the carrier generating substance include organic dyes and organic pigments. For example, those having a photosensitive layer containing a bushiazo compound are disclosed in JP-A-47-37543 and JP-A-55-2.
2834, JP-A-54-79632, JP-A-56-11604
It is already known from publication No. 0 and the like.

However, although these known bisazo compounds have relatively good sensitivity in the short wavelength region or the medium wavelength region, they have low sensitivity in the long wavelength region and are used in a laser printer using a semiconductor laser light source expected to have high reliability. It was difficult.

At present, gallium-aluminum-arsenic (Ga.Al.As) based light emitting devices that are widely used as semiconductor lasers have an oscillation wavelength of about 750 nm or more. In order to obtain an electrophotographic photosensitive member having high sensitivity to such long-wavelength light, many studies have hitherto been made. For example, Se having a high sensitivity in the visible light region, a method of adding a sensitizer for newly lengthening the wavelength of the photosensitive material such as CdS was considered, but Se and CdS are temperature and humidity as described above. There is still a problem because the environment resistance to such things is not sufficient. In addition, the sensitivity of many known organic photoconductive materials is usually limited to the visible light region of 700 nm or less as described above, and few materials have sufficient sensitivity in the longer wavelength region.

Of these, it is known that the phthalocyanine compound, which is one of the organic photoconductive materials, has a light-sensitive region expanded to a longer wavelength region than other compounds. Examples of these phthalocyanine compounds exhibiting photoconductivity include α-type titanyl phthalocyanine described in JP-A No. 61-239248. As shown in FIG. 2, this α-type titanyl phthalocyanine has peaks at a Bragg angle of 7.5, 12.3, 16.3, 25.3 and 28.7 with respect to X-ray of CuKα1.541Å. However, this α-type titanyl phthalocyanine has low sensitivity and poor potential stability against repeated use, and in the electrophotographic process using reversal development,
There are problems such as easy occurrence of ground fog. Further, since the charging ability is poor, it is difficult to obtain a sufficient image density.

By the way, generally, in a photoreceptor, a carrier-transporting substance effective for a specific carrier-generating substance is not always effective for another carrier-generating substance, and conversely for a specific carrier-transporting substance. It cannot be said that an effective carrier generating substance is also effective for other carrier transporting substances. After all, in order to be used in the electrophotographic photoreceptor, a proper combination of both the carrier-generating substance and the carrier-transporting substance is necessary. If this combination is inappropriate, the sensitivity of the electrophotographic photoreceptor is increased. Not only becomes low, but also the discharge efficiency is low especially in a low electric field, so that the so-called residual potential becomes large, and in the worst case, when the electrophotographic photoreceptor is used in a copying machine, for example, it is repeatedly used. Charge accumulates every time
For this reason, the toner may adhere to the non-image portion to cause background stain on the copy, or a clear copy image may not be obtained.

Such a combination of a carrier-generating substance and a carrier-transporting substance is important, but there is not always a general law of selection means for this combination, and it is necessary to find a carrier-transporting substance suitable for a specific carrier-generating substance. Is difficult.

C. As described above, as the organic carrier-generating substance having sensitivity in the long wavelength region, a phthalocyanine compound can be mentioned, but the α-type titanyl phthalocyanine is a production method thereof, and has a stable potential when repeatedly used as an electrophotographic photoreceptor. There is a problem with sex.

Therefore, a first object of the present invention is to provide a photoconductor using titanyl phthalocyanine, which has high sensitivity especially to light having a wavelength of 600 nm or more.

A second object of the present invention is to provide a photoreceptor using a carrier-transporting material suitable for the above titanyl phthalocyanine.

A third object of the present invention is to provide a photoreceptor having high potential stability by repeated use.

A fourth object of the present invention is to provide a photoconductor having excellent charging ability.

A fifth object of the present invention is to provide a photoconductor most suitable for the reversal development process.

D. According to the present invention, the peak of the Bragg angle 2θ for CuKα characteristic X-ray (wavelength 1.541Å) is at least 9.5 degrees ± 0.2 degrees, 9.7 degrees.
Degree ± 0.2 degrees, 11.7 degrees ± 0.2 degrees, 15.0 degrees ± 0.2 degrees, 23.5 degrees ±
A compound represented by the following general formula [I], which contains titanyl phthalocyanine having a maximum absorption peak at 27.3 degrees ± 0.2 degrees and at 0.2 degrees, 24.1 degrees ± 0.2 degrees and 27.3 degrees ± 0.2 degrees. And a compound represented by the following general formula [II].

General formula [I]: (However, in this general formula, R ^{1 is a} substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, R ^{2 is a} hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Ring group, R ³ : hydrogen atom, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group, X ¹ : hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted amino group, alkoxy group or A cyano group, X ² : represents a hydrogen atom or a substituted or unsubstituted alkyl group, p: 0 or an integer of 1. ] General formula [II] (However, in this general formula, R ^{4 is a} substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, R ^{5 is a} hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. ring group, R ^6: a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, X ^3: a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted amino group, an alkoxy group, or A cyano group, X ⁴ : represents a hydrogen atom or a substituted or unsubstituted alkyl group, q: 0 or an integer of 1. The photoreceptor of the present invention has a remarkable feature in that the specific titanyl phthalocyanine having the above-mentioned main peak of Bragg angle is used as a carrier generating substance.

That is, the titanyl phthalocyanine has a high sensitivity to light having a wavelength of 600 nm or more, as described later, and the maximum value of its photosensitive wavelength range is 817 nm ± 5 nm.
Therefore, by adopting the above-mentioned titanyl phthalocyanine, it is possible to obtain a photoreceptor having high sensitivity to light in a long wavelength region such as a light emitting diode and a semiconductor laser. Further, since the titanyl phthalocyanine has excellent charging ability, it is possible to obtain a sufficient image density, and also excellent in potential stability against repeated use, and it is difficult for fog to occur even in an electrophotographic process using reversal development. . Furthermore, the above-mentioned titanyl phthalocyanine has an extremely stable crystal form, is unlikely to cause transition to another crystal form, and has excellent crystal stability against solvent, heat and mechanical strain. Therefore, as described above, not only is it excellent in the characteristics upon repeated use, it is advantageous in the preparation of titanyl phthalocyanine, and it has great advantages in the production of an electrophotographic photoreceptor and in its use.

Further, in the photoreceptor of the present invention, at least one of the hydrazone compound represented by the above general formula [I] and the hydrazone compound represented by the above general formula [II] is contained as a carrier transport substance. It is characterized by

That is, when the combination of the carrier-generating substance and the carrier-transporting substance is inappropriate, the sensitivity is lowered, the residual potential is raised, and the potential stability during repeated use is lowered. Moreover, it is considered that there is no general law for selecting the above-mentioned combinations, and it is the actual situation that advantageous combinations are practically determined from a large number of substance groups.

Here, the present inventor has found that, when the titanyl phthalocyanine compound is used as a carrier-generating substance in a photoreceptor, if the hydrazone compound is selected as a carrier-transporting substance, a photoreceptor having good characteristics can be obtained. It was.

That is, if the carrier transporting substance of the present invention is selected, carrier injection from the carrier generating substance to the carrier transporting substance is performed smoothly, probably because the ionization potential is compatible with the titanyl phthalocyanine of the present invention. It is possible to enjoy good residual potential characteristics, sensitivity characteristics upon repeated use, and charging potential characteristics.

In addition, the hydrazone compounds represented by the above general formulas [I] and [II] according to the present invention have excellent compatibility with various polymer binders, and thus, even if the amount of the hydrazone compound with respect to the polymer binder is increased, it becomes cloudy and opaque. Since it does not occur, the mixing range of the polymer binder can be made very wide, so that a photoreceptor having preferable carrier transporting performance and physical properties can be produced. Since the compatibility is excellent, the carrier transport phase is uniform and stable, and as a result, it is possible to obtain a photoreceptor having high sensitivity and capable of forming a clear image without sensitivity, charging characteristics and fog. In addition, when it is used for repetitive transfer type electrophotography, it is possible to obtain the effect that fatigue deterioration does not occur.

Further, the carrier transport material of the present invention is safe, environmentally preferable, and chemically stable.

As described above, according to the present invention, it is possible to provide a photoreceptor having high sensitivity to long-wavelength light, high potential stability due to repeated use, and excellent chargeability in a reversal development process.

In the photosensitive layer constituting the photoreceptor of the present invention, it is preferable that the granular carrier generating substance and the carrier transporting substance are bound by the binder substance (that is, dispersed in the form of pigment in the layer). . In this case, the printing durability and durability of the layer are improved, the memory phenomenon is small, and the residual potential is stable.

When the titanyl phthalocyanine according to the present invention is used as a function-separated type electrophotographic photoreceptor, it is used as a carrier generating substance and is combined with a carrier transporting substance to form a photoreceptor. This titanyl phthalocyanine according to the present invention is different from the above-mentioned α-type titanyl phthalocyanine, and as shown in FIG. 1, CuKα1.5
Bragg angle for 41Å X-ray (error 2θ ± 0.2 degrees)
Has an X-ray diffraction spectrum having major peaks at 9.5, 9.7, 11.7, 15.0, 23.5, 24.1 and 27.3. The Bragg angles of CuKα1.541Å of α-type titanyl phthalocyanine for X-rays are 7.5, 12.3, 16.3, 25.3, 2 as described above.
Since it is 8.7, it has a completely different crystal form from the α form.

The titanyl phthalocyanine according to the present invention exhibits a unique spectrum which has never been obtained as described above, and its basic structure is represented by the following general formula.

(However, X ¹ , X ² , X ³ , and X ⁴ represent Cl or Br, and a, b,
c and d represent the integer of 0-4. The X-ray diffraction spectrum is measured under the following conditions (the same applies hereinafter). X-ray tube Cu voltage 40.0 KV current 100.0 mA start angle 6.00 deg. Stop angle 35.00 deg. Step angle 0.020 deg. Measurement time 0.50 sec. The method for producing titanyl phthalocyanine according to the present invention will be exemplified.

First, for example, titanium tetrachloride and phthalodinitrile
Dichlorotitanium phthalocyanine (TiCl ₂ Pc) obtained by reacting in a chloronaphthalene solvent
Is hydrolyzed with aqueous ammonia to obtain α-type titanyl phthalocyanine. This is followed by 2-
Treatment with an electron-donating solvent such as ethoxyethanol, diglyme, dioxane, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, morpholine is preferred.

Next, the α-type titanyl phthalocyanine is added to 50 to 180
The titanyl phthalocyanine of the present invention is produced by stirring at a temperature of 60 ° C., preferably 60 to 130 ° C. for a sufficient time for crystal conversion or milling with mechanical strain.

As another method for producing the above α-type titanyl phthalocyanine, TiCl ₂ Pc is preferably dissolved once in sulfuric acid at 5 ° C. or below or made into a sulfuric acid salt, poured into water or ice water, and reprecipitated or hydrolyzed. , Α-type titanyl phthalocyanine is obtained.

The titanyl phthalocyanine obtained as described above is preferably used in a dry state, but a water paste type can also be used. The dispersion medium for stirring and kneading may be one normally used for dispersion of pigments, emulsification and mixing, and examples thereof include glass beads, steel beads, alumina beads, and flint stone. However, the dispersion medium is not always necessary. As the grinding aid, those usually used as a grinding aid for pigments may be used, and examples thereof include common salt, sodium bicarbonate, and sodium sulfate. However, this grinding aid is not always necessary.

When a solvent is required at the time of stirring, kneading and grinding, it may be liquid at the temperature at the time of stirring and kneading, for example, alcohol solvent, that is, glycerin, ethylene glycol, diethylene glycol or polyethylene glycol solvent, ethylene glycol monomethyl. It is preferable to select at least one kind from the group of cellosolve-based solvents such as ether and ethylene glycol monoethyl ether, ketone-based solvents, esterketone-based solvents and the like.

Typical examples of the apparatus used in the crystal transition step include a general stirring apparatus such as a homomixer, a disperser, an agitator, a stirrer or a kneader, a Banbury mixer, a ball mill, a sand mill and an attritor.

The temperature range in the crystal transition step is 50 to 180 ° C, preferably 60 to 130 ° C. It is also effective to use crystal nuclei at the same time as in the normal crystal transition process.

Specific examples of the hydrazone compound represented by the above general formulas [I] and [II] include, but are not limited to, those having the following structural formulas.

In the present invention, in addition to the above titanyl phthalocyanine, another carrier generating substance may be used in combination. Carrier generating substances that can be used in combination include, for example, α type, β type, γ
Type, X type, τ type, τ ′ type, η type, η ′ type titanyl or metal-free phthalocyanine. Further, phthalocyanine pigments other than the above, azo pigments, anthraquinone pigments,
Examples thereof include perylene pigments, polycyclic quinone pigments, methine squaric acid pigments, and the like.

 Examples of the azo pigment include the followings.

(III-5) A-N = N-Ar ¹ -CH = CH-Ar ² -N = N-
A (III-6) A- N = N-Ar 1 -CH = CH-Ar 2 -N = CH-A
r ³ −N = NA (III-8) A-N = N-Ar ¹ -N = N-Ar ² -N = N-
A (III-9) A- N = N-Ar 1 -N = N-Ar 2 -N = N-A
r ³ −N = NA (However, in this general formula, Ar ¹ , Ar ² and Ar ³ : respectively, a substituted or unsubstituted carbon compound aromatic ring group, R ¹⁹ , R ²⁰ , R ²¹ and R ²² : respectively, an electron-withdrawing group or A hydrogen atom, at least one of R ^{19 to} R ^{22 being} an electron-withdrawing group such as a cyano group; (X is a hydroxy group, Or —NHSO ₂ —R ²⁶ <wherein R ²⁴ and R ²⁵ are each a hydrogen atom or a substituted or unsubstituted alkyl group, R ²⁶ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group>, Y Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxyl group, a sulfo group, a substituted or unsubstituted carbamoyl group or a substituted or unsubstituted sulfamoyl group (however, when m is 2 or more, They may be mutually different groups.) Z is an atomic group necessary for constituting a substituted or unsubstituted carbocyclic aromatic ring or a substituted or unsubstituted heterocyclic aromatic ring, and R ²³ is hydrogen. An atom, a substituted or unsubstituted amino group,
A substituted or unsubstituted carbamoyl group, a carboxyl group or an ester group thereof, Ar ⁴ represents a substituted or unsubstituted aryl group, and n represents 1
Or an integer of 2, and m is an integer of 0 to 4. )] Examples of the polycyclic quinone pigment include compounds of the following general formula [IV].

General formula (IV) (In this general formula, X'represents a halogen atom, a nitro group, a sialic group, an acyl group or a carboxy group, and n represents an integer of 0 to 4.) Specific examples are as follows.

In the photoreceptor of the present invention, as a carrier transporting material that can be used together in the case of function separation type, an oxazole derivative, an oxadiazole derivative, a thiazole derivative, a thiadiazole derivative, a triazole derivative, an imidazole derivative, an imidazolone derivative, an imidazolidine derivative,
Bisimidazolidine derivative, pyrazoline derivative, oxazolone derivative, benzothiazole derivative, benzimidazole derivative, quinazoline derivative, benzofuran derivative, acridine derivative, phenazine derivative, aminostilbene derivative, poly-N-vinylcarbazole, poly-
1-vinylpyrene, poly-9-vinylanthracene and the like can be mentioned.

In order to form the photosensitive layer of the photoreceptor of the present invention, a layer in which the above-mentioned carrier generating substance is dispersed in a binder may be provided on the conductive support. Alternatively, the carrier generating substance and the carrier transporting substance may be combined to provide a laminated or dispersed so-called function-separated photosensitive layer.
When the function-separated photosensitive layer is used, it is usually as shown in FIGS. That is, in the layer structure shown in FIG. 6, a carrier generating layer 2 containing titanyl phthalocyanine according to the present invention is formed on a conductive support 1, and a carrier transporting layer 3 containing a carrier transporting material is laminated on this. A photosensitive layer 4 is formed, and FIG. 7 is a photosensitive layer 4'in which the carrier generating layer 2 and the carrier transporting layer 3 are reversed, and the layer structure of FIG. 8 is shown in FIG. The intermediate layer 5 is provided between the photosensitive layer 4 having the layer structure and the conductive support 1, and FIG. 9 shows the intermediate layer 5 between the photosensitive layer 4 ′ having the layer structure and the conductive support 1 shown in FIG. Are provided to prevent the injection of free electrons into the conductive support 1. The layer structure shown in FIG. Photosensitive layer 4 ″ containing carrier transport material 7 It is obtained by forming,
In the layer structure shown in FIG. 11, the intermediate layer 5 is provided between the photosensitive layer 4 ″ and the conductive support 1.

The carrier generation layer 2 in the case of forming a photosensitive layer having a two-layer structure can be provided by the following method.

(A) A method in which a solution in which a carrier-generating substance is dissolved in an appropriate solvent or a solution in which a binder is added thereto and mixed and dissolved is applied.

(B) A method in which a carrier-generating substance is made into fine particles in a dispersion medium by a ball mill, a homomixer, or the like, and a binder is added, if necessary, and mixed and dispersed, and a dispersion liquid obtained by coating is applied.

In these methods, when the particles are dispersed under the action of ultrasonic waves, uniform dispersion becomes possible.

As the solvent or dispersion medium used for forming the carrier generation layer, n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, methylethylketone, cyclohexanone, benzene, toluene, Xylene, chloroform,
Examples thereof include 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like.

When a binder is used for forming the carrier generation layer or the carrier transport layer, any binder can be used as the binder. Particularly, a polymer that is hydrophobic and has a high dielectric constant and an electric insulating film-forming ability. Polymers are preferred. Examples of such polymers include, but are not limited to, the followings.

a) Polycarbonate b) Polyester c) Methacrylic resin d) Acrylic resin e) Polyvinyl chloride f) Polyvinylidene chloride g) Polystyrene h) Polyvinyl acetate i) Styrene-butadiene copolymer j) Vinylidene chloride-acrylonitrile copolymer k) Vinyl chloride-vinyl acetate copolymer 1) Vinyl chloride-vinyl acetate-maleic anhydride copolymer m) Silicon resin n) Silicon-alkyd resin o) Phenol-formaldehyde resin p) Styrene-alkyd resin q) Poly-N- Vinylcarbazole r) Polyvinyl butyral s) Polycarbonate Z resin These binders can be used alone or as a mixture of two or more kinds. The ratio of the carrier-generating substance to the binder is 10 to 600% by weight, preferably 5
It is preferable that the amount of carrier transport material is 0 to 400% by weight and the amount of carrier transport material is 10 to 500 parts by weight.

The thickness of the carrier generation layer 2 thus formed is
The thickness is preferably 0.01 to 20 μm, more preferably 0.05 to 5 μm. The thickness of the carrier transport layer is 2-10
It is 0 μm, preferably 5 to 30 μm.

When the photosensitive layer is formed by dispersing the carrier-generating substance, the carrier-generating substance is preferably a powder having an average particle diameter of 2 μm or less, preferably 1 μm or less. That is, if the particle size is too large, the dispersion in the layer becomes poor, and the particles partially project on the surface to deteriorate the smoothness of the surface, and in some cases discharge occurs at the projecting part of the particle, or there is Toner particles tend to adhere to cause a toner filming phenomenon. A carrier-generating substance that is sensitive to long-wavelength light (up to 700 nm) has a large particle size because the surface charge is neutralized by the generation of thermally excited carriers in the carrier-generating substance. It seems that the neutralizing effect is great. Therefore, high resistance and high sensitivity can be achieved only by reducing the particle size.

Further, the photosensitive layer may contain one or more electron-accepting substances for the purpose of improving sensitivity, reducing residual potential or reducing fatigue during repeated use. Examples of the electron-accepting substance that can be used here include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, and 4-nitrophthalic anhydride. Nitrophthalic anhydride, Pyromellitic anhydride, Mellitic anhydride, Tetracyanoethylene, Tetracyanoquinodimethane, o-
Dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bulmannyl, dichlorodicyanoparabenzoquinone, anthraquinone, dinitroanthraquinone, 9-fluorenylidene [dicyanomethylene Malonodiitryl], polynitro-9-fluorenylidene- [dicyanomethylene malonodinitrile], picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitro Examples thereof include salicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, mellitic acid, and other compounds having a high electron affinity. Further, the addition ratio of the electron-accepting substance is 100: 0.01 to 200, preferably 100: 0.1 to 100 for the carrier-generating substance: electron-accepting substance in a weight ratio.
Is.

The support 1 on which the photosensitive layer is provided is a metal plate,
A conductive thin layer made of a metal drum, a conductive polymer, a conductive compound such as indium oxide, or a metal such as aluminum, palladium, or gold is provided on a substrate such as paper or a plastic film by a method such as coating, vapor deposition, or laminating. Is used. The intermediate layer functioning as an adhesive layer or a barrier layer is composed of a polymer such as the above-described binder resin, an organic polymer such as polyvinyl alcohol, ethyl cellulose, and carboxymethyl cellulose, or aluminum oxide. Things are used.

E. Examples Hereinafter, examples of the present invention will be described. First, the synthesis example 1 of the titanyl phthalocyanine according to the present invention and α of Comparative Example
2 shows Synthesis Examples 2 and 3 of type titanyl phthalocyanine.

(Synthesis Example 1) 10 parts of α-type titanyl phthalocyanine, 5 to 20 parts of salt as a grinding aid, and 10 parts of (polyethylene glycol) as a dispersion medium were put in a sand grinder, and the temperature was 60 ° C to 120 ° C.
It was ground for 7 to 15 hours. In this case, if the graining is performed at a high temperature, the β-type crystal form is likely to be exhibited and the decomposition is likely to occur. After taking out from the container and removing the grinding aid and the dispersion medium with water and methanol, the product was purified with a 2% dilute sulfuric acid aqueous solution, filtered, washed with water and dried to obtain a clear greenish blue crystal. This crystal was found to be the titanyl phthalocyanine of the present invention in FIG. 1 by X-ray diffraction and infrared spectroscopy.

The infrared absorption spectrum was as shown in FIG. The maximum wavelength (λmax) of the absorption spectrum is 817
However, this is different from λmax = 830 nm of α-type titanyl phthalocyanine.

(Synthesis Example 2) A mixture of 40 g of phthalodinitrile, 18 g of titanium tetrachloride and 500 ml of α-chloronaphthalene was heated and stirred under a nitrogen stream at 240 to 250 ° C for 3 hours to complete the reaction. Then, the product was filtered to obtain the product dichlorotitanium phthalocyanine. A mixture of the obtained dichlorotitanium phthalocyanine and 300 ml of concentrated aqueous ammonia was heated under reflux for 1 hour,
18 g of the target product, titanyl phthalocyanene, was obtained. The product was thoroughly washed with acetone in a Soxhlet extractor. This product was α-type titanyl phthalocyanine shown in FIG.

(Synthesis Example 3) The titanyl phthalocyanine of Synthesis Example 2 was treated with an acid paste to obtain α-type titanyl phthalocyanine having the spectrum shown in FIG.

<Production of Photoreceptor> Next, production of the photoreceptors of Examples and Comparative Examples will be described.

(Examples 1 to 8) 1 part of the titanyl phthalocyanine of the present invention of Synthesis Example 1, a binder resin for dispersion, a polyvinyl butyral resin ("XY
1 part of HL "manufactured by Union Carbide Co., Ltd.) and 100 parts of tetrahydrofuran were dispersed for 15 minutes using an ultrasonic disperser. The obtained dispersion liquid was applied with a wire bar onto a conductive support made of a polyester film on which aluminum was vapor-deposited to form a carrier generation layer having a thickness of 0.2 μm.

On the other hand, the compounds shown in Table 1 below (carrier transport substances)
3 parts and polycarbonate resin ("Panlite L-1250"
Teijin Kasei Co., Ltd.) 4 parts was dissolved in 30 parts of 1,2-dichloroethane, and the resulting solution was applied onto the carrier generating layer and dried to form a carrier transporting layer having a thickness of 18 μm. An electrophotographic photoreceptor of the present invention was prepared.

Comparative Example 1 An electrophotographic photosensitive member similar to that of Example 1 was prepared except that the carrier transporting material of Example 1 was replaced by the carrier transporting material having the following structure.

(Comparative Example 2) An electrophotographic photosensitive member similar to that of Example 1 was prepared except that the carrier transporting material having the following structure was used instead of the carrier transporting material of Example 1. The spectral sensitivity distribution of this photoconductor is the fifth
As shown in the figure, the long wavelength sensitivity was good.

(Comparative Example 3) In the same manner as in Example 1 except that the carrier-generating substance having the X-ray diffraction spectrum diagram shown in FIG. A comparative photoconductor was prepared.

(Comparative Example 4) In the same manner as in Example 1 except that the carrier-generating substance having the X-ray diffraction spectrum shown in FIG. A comparative photoconductor was prepared.

(Example 9) On a polyester laminated with aluminum foil,
Thickness 0.1 made of vinyl chloride-vinyl acetate-maleic anhydride copolymer (S-REC MF-10, Sekisui Chemical Co., Ltd.)
A μm intermediate layer was formed.

Next, the titanyl phthalocyanine of the present invention was ground as a CGM for 24 hours with a ball mill, and a 1,2-dichloroethane solution containing 6% by weight of a polycarbonate resin (Panlite L-1250, Teijin Chemicals Ltd.) was titanyl phthalocyanine / polycarbonate resin = 30/100 (weight ratio) was added, and the mixture was further dispersed by a ball mill for 24 hours. To this dispersion, 75% by weight of the carrier-transporting substances shown in Table 1 below was added to the polycarbonate resin, and further prepared so that monochlorobenzene / 1,2-dichloroethane = 3/7 (volume ratio). Was coated on the above intermediate layer by a spray coating method to form a photosensitive layer having a thickness of 20 μm to obtain a photosensitive pair sample of the present invention.

Example 10 An intermediate layer exactly the same as in Example 1 was formed on a polyester film laminated with aluminum foil.

Then, the carrier transport material / polycarbonate resin (Panlite L-1250, manufactured by Teijin Chemicals Ltd.) shown in Table 1 below =
1,2-dichloroethane solution containing 16.5% by weight of 60/100 (weight ratio) is dip-coated on the intermediate layer and dried,
A 15 μm thick CTL was obtained.

Next, the titanyl phthalocyanine of the present invention was ground as a CGM for 24 hours by a ball mill to contain 6% by weight of a polycarbonate resin (Panlite L-1250, manufactured by Teijin Chemicals Ltd.).
Add 1,2-dichloroethane solution to titanyl phthalocyanine /
Polycarbonate resin was added in an amount of 30/100 (weight ratio) and further dispersed by a ball mill for 24 hours. To this dispersion, 75% by weight of the carrier-transporting substance shown in Table 1 below was added to the polycarbonate resin, and monochlorobenzene was further added to give monochlorobenzene / 1,2-dichloroethane = 3/7 (volume ratio). The thus-prepared product was applied onto the CGL by a spray application method to form a CTL having a thickness of 5 μm to obtain a photoreceptor sample of the present invention.

<Measurement of Characteristics of Photoreceptor> 14 kinds of photoreceptors of Examples 1 to 10 and Comparative Examples 1 to 4 were mounted on a modified machine of a laser printer LP-3010 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and an initial unexposed portion potential (V _H ), the exposed portion potential (V _L ), and the differences ΔV _H and ΔV _L from the initial values of V _H and V _L after 10,000 copies were measured. The table shows Δ | V _H | and Δ | V _L |.

When the amount of light required to change the charging potential ± 600 V to ± 300 V is I ₀ (erg / cm ² ), And

A semiconductor laser (oscillation wavelength 780n
m) was used.

 The formulations and measurement results of each photoconductor are shown in the table below.

The electrophotographic photosensitive member using the carrier-generating substance and carrier-transporting substance of the present invention has good long-wavelength sensitivity, high chargeability, excellent potential stability upon repeated use, and provides a clear image without fog.

On the other hand, the comparative sample has a large decrease in sensitivity and chargeability after repeated use, which causes a decrease in image density and fog.

 Next, an example applied to the reversal development process will be described.

The toner was attached to a modified machine of the four types of photoconductor laser printer LP-3010 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) of Examples 1 and 2 and Comparative Examples 1 and 3 described above, and positive or negative toner was respectively charged with positive or negative charges. Reverse development using a two-component developer containing
The image formation was repeated 00 times, and the image density and the amount of black spots on the white background were each set to "◎", "○", and "x".
Judgment was made at each stage, and the results are shown in Table 2 below. A semiconductor laser (780 nm) and LED (680 nm) are used as the light source.
Was used.

However, the amount of black spots was 0 / cm ² ○ 3 / cm ² or less × 3 / cm ² or more The image density was measured with a Sakura Densitometer PDA-65 type.

⊚ Reflection Density of 1.0 or More ○ Reflection Density of 0.6 to 1.0 × Reflection Density of 0.6 or Less As described above, it can be seen that the photoreceptor according to the present invention is suitable for reversal development.

BRIEF DESCRIPTION OF THE DRAWINGS The drawings illustrate the present invention. FIG. 1 is an X-ray diffraction diagram of the titanyl phthalocyanine of the present invention, and FIGS. 2 and 3 are α-type titanyl phthalocyanines. X-ray diffraction diagrams of two examples, FIG. 4 is an absorption spectrum of the titanyl phthalocyanine of the present invention, FIG. 5 is a spectral sensitivity diagram of the photoconductor, FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 11 and 11 are cross-sectional views showing specific examples of the layer structure of the electrophotographic photoreceptor of the present invention. In the drawings, reference numerals 1 ... Conductive support 2 ... Carrier generation layer 3 ... Carrier transport layer 4, 4 ′, 4 ″ ... Photosensitive layer 5 ... Intermediate layer.

Claims (1)

(57) [Claims] 1. The peak of Bragg angle 2θ for CuKα characteristic X-ray (wavelength 1.541Å) is at least 9.5 ° ± 0.2 °, 9.7 °
Degree ± 0.2 degrees, 11.7 degrees ± 0.2 degrees, 15.0 degrees ± 0.2 degrees, 23.5 degrees ±
A compound represented by the following general formula [I], which contains titanyl phthalocyanine having a maximum absorption peak at 27.3 degrees ± 0.2 degrees and at 0.2 degrees, 24.1 degrees ± 0.2 degrees and 27.3 degrees ± 0.2 degrees. A photoconductor containing at least one of the compounds represented by the following general formula [II]. General formula [I] (However, in this general formula, R ^{1 is a} substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, R ^{2 is a} hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Ring group, R ³ : hydrogen atom, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group, X ¹ : hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted amino group, alkoxy group or Cyano group, X ² : hydrogen atom or substituted or unsubstituted alkyl group, p: 0 or an integer of 1. General formula [II] However, in this general formula, R ^{4 is a} substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, R ^{5 is a} hydrogen atom, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Group, R ⁶ : hydrogen atom, substituted or unsubstituted alkyl group, or substituted or unsubstituted aryl group, X ³ : hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted amino group, alkoxy group or cyano Group, X ⁴ : represents a hydrogen atom or a substituted or unsubstituted alkyl group, q: 0 or an integer of 1.