JPH0629975B2 - Multilayer type photoconductor for electrophotography - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor, and more specifically, it has high photosensitivity in a wide wavelength range from visible light to near infrared light, The present invention relates to a long-wavelength photosensitive photosensitive laminated electrophotographic photoreceptor suitable for a laser beam printer or the like using a semiconductor laser as a light source.

[Prior Art] A phthalocyanine compound may exhibit photoconductivity in 1968.
Since its discovery in 1980, a great deal of research has been conducted on photoelectric conversion materials. In recent years, with the development of non-impact printing technology, research and development of a laser beam printer using a semiconductor laser as a writing head has been actively conducted. In the laser beam printer used in the electrophotographic method, first, a photosensitive drum that is uniformly charged with corona is scanned and exposed with a laser beam that is modulated based on an input signal to form an electrostatic latent image, and then toner development and transfer are performed. As a result, image formation is performed. The image quality is improved by such a laser recording system, and particularly, the use of the semiconductor laser brings advantages such as simplification of the apparatus, downsizing, and cost reduction.

At present, most of the oscillation wavelengths of semiconductor lasers that operate stably are in the near infrared region (λ> 780 nm). Therefore, the recording photoconductor used for it must have high sensitivity in the long wavelength region of 780 nm or more. In this case, the half-exposure amount of monochromatic infrared light irradiation required for practical sensitivity Is less than 10 erg / cm ² . Among such photoconductive substances exhibiting high sensitivity in the long wavelength region, phthalocyanine compounds have been particularly attracting attention.

Conventionally, for electrophotographic photoreceptors, inorganic compounds such as selenium, tellurium, cadmium sulfide, and zinc oxide, or poly N.
-Organic compounds such as vinylcarbazole and bisazo pigments are used. However, these cannot be said to have sufficient photosensitivity in the long wavelength region of 780 nm to 900 nm where many semiconductor laser light wavelengths exist, and in recent years,
It has been reported that photoreceptors using alloys of selenium, tellurium, and arsenic or photoreceptors using dye-sensitized cadmium sulfide have high sensitivity in a long wavelength region around 800 nm, but they all have strong toxicity. Environmental safety as a social problem is being reviewed. In addition, it is considered that the photosensitive region using amorphous silicon may extend the photosensitive region to the long wavelength region by a specific doping method and manufacturing method, but at this stage the film forming speed is slow and there is a problem in mass productivity, so it is low cost. It is hard to say that it is a photoconductor. Among the phthalocyanine compounds studied so far, as compounds showing high sensitivity in the long wavelength region of 780 nm or more,
Examples include χ type metal-free phthalocyanine, ε type copper phthalocyanine, vanadyl phthalocyanine and the like.

On the other hand, in order to improve the sensitivity, a laminated type photoreceptor using a vapor-deposited film of phthalocyanine as a charge generation layer has been studied, and the periodic table III
Among the phthalocyanines containing a group a metal and a group IV metal as a central metal, some having a relatively high sensitivity have been obtained. Documents relating to such metal phthalocyanines include, for example, JP-A-57-211149, 57-148745, and 59-3625.
4, 59-44054, 59-30541, 59-31965, 59-3625
4 and the same 59-166959.

[Problems to be solved by the invention]

However, a high-vacuum exhaust device is required for forming the vapor-deposited film, and the equipment cost is high, so that the organic photoreceptor as described above is inevitably expensive.

On the other hand, according to the method of forming a photosensitive layer by coating a resin solution in which phthalocyanine is dispersed, the manufacturing is easy and the manufacturing cost can be reduced, but in many cases, it is difficult to manufacture a high-sensitivity photosensitive member. According to this method, a multi-layer type photoconductor in which a charge generating layer is formed by coating a conductive substrate with a resin solution in which phthalocyanine is dispersed, and a charge transporting layer is coated thereon is being studied. As such a laminated type photoreceptor, there are those using metal-free phthalocyanine (JP-A-58-182639) and indium phthalocyanine (JP-A-59-155851), the former being 8
Although it has a relatively high sensitivity in the wavelength range of 00 nm or less, it has a drawback that the sensitivity sharply decreases in the long wavelength range of 800 nm or more, and the latter has a drawback that the sensitivity is insufficient for practical use. have.

The problem to be solved by the present invention is to improve the above-mentioned problems of the prior art,
Visible light to near-infrared light in the wavelength range of 500 to 900 nm, especially many semiconductor laser light wavelengths of 800 to 90
An object is to provide an electrophotographic photoreceptor having high photosensitivity in a long wavelength region of 0 nm.

[Means for solving problems]

The present invention relates to a laminated electrophotographic photoreceptor comprising a conductive support and a charge generation layer and a charge transport layer provided thereon. The charge generation layer is formed by dispersing α-type titanyl phthalocyanine in a binder. The above problems are solved by using layers.

The α-form titanyl phthalocyanine used in the present invention is α
Means titanyl phthalocyanine having a crystalline form of
Although various nuclear substitution products are included, more preferable ones for solving the above problems are those represented by the general formula: (In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent Cl or Br, and nm, l and k are each independently 0 or 1 to 4;
Represents the integer. ) Is an α form of titanyl phthalocyanine.

Among the α-form titanyl phthalocyanines used in the present invention, particularly preferable one is titanyl phthalocyanine (TiOP
c), titanyl chlorophthalocyanine (TiOPcCl) and mixtures thereof.

The α-form titanyl phthalocyanine used in the present invention is, for example, dichlorotitanium phthalocyanine (TiCl ₂ Pc) obtained by reacting titanium tetrachloride and phthalodinitrile in an α-chloronaphthalene solvent or titanium tetrafluoride and phthalodinitrile. Dibromotitanyl phthalocyanine (TiBr ₂ Pc) obtained by reaction in α-chloronaphthalene solvent
Is hydrolyzed in aqueous ammonia containing a hydrogen halide scavenger such as pyridine and amine, and subsequently 2-ethoxyethanol, diglyme, dioxane, tetrahydrofuran, N, N-dimethylformamide, N-methylpyrrolidone, pyridine, morpholine, etc. It can be manufactured by treating with an electron-donating solvent.

The α-form titanyl phthalocyanine thus obtained is
An X-ray diffraction pattern using Cu-Ka line is shown in FIG. This α-form titanium phthalocyanine has an X-ray diffraction pattern of 7.6
°, 10.2 °, 12.6 °, 13.2 °, 15.1 °, 16.2 °, 17.2
It has a characteristic peak at each Bragg angle 2θ (including an error range of ± 0.2) of °, 18.3 °, 22.5 °, 24.2 °, 25.3 °, 28.6 °.

When the hydrogen halide scavenger is not used in the hydrolysis reaction, according to the acid paste method, the hydrolysis product is dissolved in concentrated sulfuric acid, the solution is poured into ice water, and the resulting precipitate is collected by filtration, The α-type titanyl phthalocyanine can be produced by the washing method. The acid paste method is well known as a general method for producing α-type phthalocyanine, and is described, for example, in “Phthalocyanine Compound” by Moser and Thomas (published in 1963). The α-type titanyl phthalocyanine produced by the acid paste method has a very small crystal size, so that the characteristic peaks in the X-ray diffraction pattern are not sharp as shown in FIG. When it is treated with a solvent, its X-ray diffraction pattern becomes as sharp as in FIG. 1, and the photoconductive property is also α-type titanyl phthalocyanine produced by the above method using a hydrogen halide scavenger. Is equivalent.

The α-type titanyl phthalocyanine used in the present invention has the common specific peak in the X-ray diffraction pattern thereof, regardless of the difference in the halogen atom or the substitution position or the substitution number.

It is preferable that the α-form titanyl phthalocyanine is sufficiently ground until it becomes fine particles by a grinding device such as a ball mill, a sand mill or an attritor before use. At that time, glass beads, steel beads, and alumina beads that are usually used can be used as a grinding agent, and if necessary, salt,
A grinding aid such as sodium bicarbonate may also be used. Further, when a dispersion medium is required at the time of milling, a liquid at the temperature of milling is preferable, and for example, 2-ethoxyethanol, diclime, dioxane, tetrahydrofuran, N,
A solvent that does not promote the change of crystal form, such as N-dimethylformamide, N-methylpyrrolidone, pyridine, morpholine or polyethylene glycol can be used.

As the binder constituting the charge generation layer, various resins generally used as a binder for electrophotographic photoreceptors can be used, and preferred examples include a phenol resin,
Urea resin, melamine resin, epoxy resin, silicon resin, vinyl chloride-vinyl acetate copolymer, xylene resin,
Urethane resin, acrylic resin, polycarbonate resin,
Examples thereof include polyacrylate resin, saturated polyester resin, phenoxy resin and the like.

The charge transport layer is composed of a hole transport material and a binder. Examples of the hole transport material include a pyrazole compound, a pyrazoline compound, an oxadiazole compound, a thiazole compound, an imidazole compound, a hydrazone compound,
Aromatic amine compounds, triphenylmethane compounds,
Various hole-transporting substances belonging to poly-N-vinylcarbazole and the like can be mentioned. As the binder constituting the charge transport layer, the above resins exemplified as the binder for the charge generation layer can be used.

Among the above hole transport materials, hydrazone compounds and aromatic amine compounds are even more preferable, and the following general formula (I)
The hydrazone compound having an indoline ring represented by, the hydrazone compound having a quinoline ring represented by the following general formula (II) and the amine compound represented by the following general formula (III) are particularly preferable.

General formula (In the formula, R ₁ represents an alkyl group, an aralkyl group or an aryl group which may have a substituent, and R ₂ and R ₃ may each independently have a hydrogen atom, a halogen atom or a substituent. Represents an alkyl group, an aralkyl group or an aryl group, R ₄ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group or an aralkyl group,
R ₅ and R ₆ each independently represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, and R ₅ and R ₆
May be integrated with each other to form a ring. ) A hydrazone compound represented by.

General formula (In the formula, B represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom or a substituent. Represents an alkyl group, an aralkyl group or an aryl group which may have a hydrazone compound.

General formula (In the formula, Ar ₁ , Ar ₂ and Ar ₃ represent a substituted or unsubstituted aromatic carbocyclic group or aromatic heterocyclic group).

Next, specific examples of the compounds represented by the above general formulas (I), (II) and (III) are listed in Tables 1, 2 and 3, respectively.

Since the electrophotographic photoreceptor according to the present invention has a high spectral sensitivity over the entire wavelength range of about 500 to 900 nm, it can be used not only as a photoreceptor for a semiconductor laser printer but also as a photoreceptor for an ordinary copying machine. However, about 500 nm
In the following short wavelength region, since the spectral sensitivity decreases as the wavelength decreases, it is necessary to use as a photoconductor for a color copying machine in a short wavelength region of about 500 nm or less,
In particular, it is necessary to enhance the spectral sensitivity in the wavelength region of about 400 to 500 nm. In that case, it is effective to add other charge generating substances such as bisazo compounds and perylene compounds together with α-type titanyl phthalocyanine into the charge generating layer. The suitable addition amount of these compounds is 10 to 70% by weight, preferably 30 to 50% by weight, based on the charge generation layer.

Specific preferred examples of bisazo compounds are listed in Table 4.

Examples of the perylene-based compound effective for improving the spectral sensitivity of the photoconductor in the short wavelength region of about 500 nm or less include general formulas (Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkylaryl group or amino group). .

Preferred specific examples of perylene compounds are listed in Table 5.

The electrophotographic photoreceptor of the present invention can be obtained, for example, by adding the above-mentioned finely divided α-type titanyl phthalocyanine to a solution of a resin dissolved in a suitable organic solvent and adding a conventional dispersing machine (ball milling, paint shaker, red devil). , An ultrasonic disperser or the like), and the resultant is coated on a conductive support and dried to prepare. For coating, a roll coater, wire bar, doctor blade or the like is usually used.

Suitable solvents include, for example, aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and butanone; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as ethyl ether; tetrahydrofuran and dioxane. Examples thereof include cyclic ethers; esters such as ethyl acetate and methyl cellosolve acetate, and one or more of these can be used.

3 and 4 show the sectional structure of the electrophotographic photoreceptor of the present invention. In the photoreceptor of FIG. 3, the charge generation layer 5 is provided on the conductive support 1, and the charge transport layer 6 is provided thereon.
Are laminated. The charge generation layer 5 is formed by dispersing α-type titanyl phthalocyanine 2 in the binder 3, and the charge transport layer 6 is formed by dissolving or dispersing the hole transport substance 4 in the binder 3. is there. The photoreceptor shown in FIG. 4 is one in which a charge transport layer 6 is provided on a conductive support 1 and a charge generation layer 5 is laminated thereon, and the configurations of both layers are the same as described above.

In each of the photoreceptors shown in FIGS. 3 and 4, the thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.01 μm or less.
˜2 μ, and the thickness of the charge transport layer is preferably 3 to 5
It is 0 μ, and more preferably 5 to 20 μ.

The proportion of the α-form titanyl phthalocyanine compound in the electrophotographic photoreceptor of the present invention is 0.05 to 90% by weight, preferably 15 to 50% by weight, based on the charge generating layer, and the proportion of the hole transporting material is the charge transporting layer. It is 10 to 90% by weight, preferably 10 to 60% by weight, based on the layer. In the production of the photoconductor of the present invention, a plasticizer can be used together with the binder.

For the conductive support of the photoreceptor of the present invention, for example, a metal plate or metal foil such as aluminum, a plastic film on which a metal such as aluminum is deposited, or a paper subjected to a conductive treatment is used.

The photoreceptor of the present invention may be provided with an adhesive layer or a barrier layer between the conductive support and the photosensitive layer, if necessary.
Polyamide, nitrocellulose, casein, polyvinyl alcohol and the like can be used as the material for these layers, and the film thickness is preferably 1 μm or less.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

The charge transport substance No. or charge generating substance No. in the examples represents the compound No. described in Tables 1 to 5 above.

All "parts" in each example represent "parts by weight" unless otherwise specified.

〔Example〕

I. Production of α-form titanyl phthalocyanine 40 g of phthalodinitrile, 18 g of titanium tetrachloride and α-
Chloronaphthalene 500m mixture under nitrogen stream 24
The reaction was completed by heating with stirring at 0 to 250 ° C. for 3 hours.
Then, the product was passed through to obtain a product, dichlorotitanium phthalocyanine. The obtained dichlorotitanium phthalocyanine was added to concentrated ammonia water 300 m and pyridine 300
The mixture was heated under reflux with m for 1 hour to obtain 18 g of the desired product, α-form titanyl phthalocyanine. The product was thoroughly washed with acetone in a Soxhlet extractor.

Mass spectrometric analysis of this product revealed that it contained titanyl phthalocyanine (M ⁺ 576) as a main component and a small amount of chlorinated titanyl phthalocyanine (M ⁺ 610). FIG. 1 is an X-ray diffraction diagram of this α-form titanyl phthalocyanine.

II. Production of Electrophotographic Photoreceptor Example 1 α-form titanyl phthalocyanine obtained according to I above (5 parts)
Was pulverized with a ball mill using alumina beads (60 parts) for 64 hours. The finely divided titanyl phthalocyanine 3 parts, saturated polyester resin (“Vylon 200”
(Manufactured by Toyobo Co., Ltd.) 1 part and 210 parts of chloroform are mixed in a ball mill using alumina beads for 18 hours, and the obtained dispersion is applied on an aluminum vapor-deposited polyester film with a wire bar to give a dry film thickness of 0.3 μm. A generator layer was formed. On top of this charge generation layer, the charge transport material NoT-
16 (5 parts), polycarbonate resin ("Panlite-
1250W "Teijin Kasei Co., Ltd. 5 parts chloroform 6
A solution dissolved in 5 parts was applied with a wire bar to form a charge transport layer having a dry film thickness of 10 μm, to prepare a laminated electrophotographic photoreceptor.

The sensitivity of this photoreceptor is "Paper Analyzer-SP-428".
(Kawaguchi Denki Seisakusho Co., Ltd.) is used to initially charge the photoconductor in the dark by corona discharge with an applied voltage of -6 kV to obtain an initial potential.
(V ₀ ) was measured, then left in the dark for 10 seconds, and the surface potential retention rate (V ₁₀ / V ₀ ) after 10 seconds was measured. Then, the photosensitivity E1 / 2 and E1 / 5 were measured by a method of irradiating light from a tungsten lamp at a surface illuminance of 5 lux and measuring the time until the surface potential decreased to 1/2 or 1/5. .

Similarly, the surface potential (V ₁₅ ) 15 seconds after the start of exposure
Also measured.

Further, the light separated into 830 nm (light intensity 10 mw / m ² ) was irradiated and measured, and similarly the photosensitivity (E1 / 2, E1 / 5) was measured.

The spectral sensitivity of this photoconductor is 520 to 9 as shown in FIG.
In a wide range of 00 nm, the practical sensitivity E1 / 2 = 10 erg / cm ² (E1 / 2 ^-1 = 0.1 cm ² / erg) of the photoconductor for a laser printer is exceeded.

FIG. 6 is an X-ray diffraction diagram of this photoconductor.

Further, the same layer as the charge generation layer of this photoreceptor was applied and formed on a transparent PET film. FIG. 7 is the visible absorption spectrum.

Example 2 The α-form titanyl phthalocyanine obtained in I above was ground in the same manner as in Example 1 to dissolve 1 part of finely divided titanyl phthalocyanine in 10 parts of concentrated sulfuric acid while maintaining it at 5 ° C., followed by stirring for 2 hours. Continued. This solution was gradually added dropwise to 200 parts of ice water and stirred, and the precipitate was thoroughly washed with distilled water.
The X-ray diffraction pattern of the α-form titanyl phthalocyanine thus obtained is shown in FIG. The α-type titanyl phthalocyanine was ground with a ball mill using alumina beads for 20 hours, and the ground α-type titanyl phthalocyanine was used to prepare a laminated electrophotographic photoreceptor in the same manner as in Example 1, The characteristics of the photoconductor were measured.

Comparative Example 1 Using β-type titanyl phthalocyanine obtained by recrystallizing and refining the α-type titanyl phthalocyanine obtained in I above by α-chloronaphthalene, a laminated electrophotographic photoreceptor was prepared in the same manner as in Example 1. Then, the spectral sensitivity characteristic of the photosensitive layer was specified.

Further, the same layer as the charge generation layer of the above Comparative Example was applied on a PET film, and its visible absorption spectrum was measured.

FIG. 8 is an X-ray diffraction pattern of β-type titanyl phthalocyanine. The spectral sensitivity characteristics of the photoreceptor of Comparative Example 1 are shown in FIG. 5, and the visible absorption spectrum of the charge generation layer is shown in FIG. 7 by a dotted line.

As is clear from FIGS. 5 and 7, the photoconductor of the present invention using α-type titanyl phthalocyanine is 8% less than the photoconductor of the comparative example using β-type titanyl phthalocyanine.
It is clearly superior in spectral sensitivity characteristics and absorption characteristics in the long wavelength region of 00 nm or more.

Example 3 A solution containing a charge transport material NoT-16 (8 parts), a polyarylate resin ("U100" manufactured by Union Carbide Co., Ltd.) (8 parts), and 92 parts of dioxane was vapor-deposited with aluminum to a dry film thickness of 10 µ. It was applied onto a polyester film and dried. In addition, 3 parts of finely divided α-type titanyl phthalocyanine obtained by the same method as in Example 1 and a charge generating substance
NoP-53 (1 part), charge transport material NoT-16 (6
Part), polyarylate resin “U100” (15 parts) and 150 parts of chloroform were mixed with a paint shaker and then coated so as to have a dry film thickness of 5 μm to prepare a laminated electrophotographic photoreceptor. The photoreceptor characteristics were measured and summarized in Table 6.

The characteristics of the photoconductors of Examples 1 to 3 and Comparative Example 1 are summarized in Table 6.

Examples 4 to 7 3 parts of micronized titanyl phthalocyanine obtained in the same manner as in Example 1, saturated polyester resin (“Vylon 20
0 "(manufactured by Toyobo Co., Ltd.) and various solvents 2 in Table 7 below.
10 parts were mixed by a ball mill using alumina beads for 18 hours, and the resulting dispersion was coated on an aluminum vapor-deposited polyester film with a wire bar and dried to give a dry film thickness of 0.1.
A 3 μ charge generation layer was formed. A laminated type electrophotographic photoconductor was prepared in the same manner as in Example 1 except for the above, and was set to 830 nm.
The sensitivity (E1 / 5) of the photoconductor was measured by irradiating the light (light intensity 10 mw / m ² ) which was spectrally separated into 10 and summarized in Table 7.

Examples 8 to 14 In Example 1, various photoconductors were prepared by using the other charge transport substances shown in Table 8 in place of the charge transport substance NoT-16. The light (light intensity 10 mw / m ² ) dispersed at 830 nm was incident on the photoconductor to measure the sensitivity (E 1/5) of the photoconductor, and the results are shown in Table 8.

Examples 15 to 20 In the photoconductor of Example 1, various photoconductors were prepared by adding the charge generating substance shown in Table 9 in the charge generating layer to the α-type titanyl phthalocyanine in an amount of 30% by weight. The characteristics of each photoreceptor are summarized in Table 9.

[Effects of the Invention] The laminated electrophotographic photoreceptor of the present invention has a high sensitivity in a wide wavelength range of 520 to 900 nm by having a photosensitive layer in which α-type titanyl phthalocyanine is dispersed in a binder. In particular, it is excellent as a photoconductor for a laser beam printer or a liquid crystal printer using a light source of about 700 to 900 nm.

The laminated electrophotographic photoreceptor of the present invention is not limited to a laser beam printer, but may be a semiconductor laser or the like at 750 to 850 nm.
It can also be applied to various other optical recording devices using the above light source.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction pattern of α-form titanyl phthalocyanine. FIG. 2 is an X-ray diffraction pattern of α-type titanyl phthalocyanine treated by the acid paste method. 3 and 4 are enlarged partial sectional views of the electrophotographic photosensitive member according to the present invention. 1 ... Conductive support, 2 ... Titanyl phthalocyanine, 3 ...
Binder, 4 ... Hole transporting material, 5 ... Charge generating layer, 6 ... Charge transporting layer. FIG. 5 is a graph showing the spectral sensitivity of the electrophotographic photoconductors of Example 1 and Comparative Example 1. FIG. 6 is a graph showing the spectral sensitivity of the charge generation layer of the photoconductor of Example 1. FIG. 7 is a diagram showing visible absorption spectra of the charge generation layers of the electrophotographic photoreceptors of Example 1 and Comparative Example 1. FIG. 8 is an X-ray diffraction pattern of β-type titanyl phthalocyanine.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-166959 (JP, A) JP-A-60-26947 (JP, A) JP-A-59-49544 (JP, A) JP-A-59- 214034 (JP, A) JP-A-60-95441 (JP, A)

Claims (12)

[Claims] 1. In a laminated type electrophotographic photoreceptor comprising a conductive support and a charge generation layer and a charge transport layer provided thereon, the charge generation layer is of the general formula (In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently Cl.
Or Br, and n, m, l and k are each independently 0.
Alternatively, it represents an integer of 1 to 4. (3) A laminated type electrophotographic photosensitive member having a charge generation layer formed by dispersing α-type titanyl phthalocyanine represented by the formula (1) in a binder. 2. The α-form titanyl phthalocyanine has an X-ray diffraction pattern of 7.6 °, 10.2 °, 12.6 °, 13.2 °, 15.1 °, 1
6.2 °, 17.2 °, 18.3 °, 22.5 °, 24.2 °, 25.3 ° and 2
The laminated electrophotographic photoreceptor according to claim 1, which is α-type titanyl phthalocyanine having a peak at each Bragg angle 2θ of 8.6 °. 3. A charge generation layer containing a bisazo compound together with α-form titanyl phthalocyanine.
The laminated type electrophotographic photoreceptor of the item. 4. A charge generation layer containing a perylene-based compound together with α-type titanyl phthalocyanine.
The laminated type electrophotographic photoreceptor of the item. 5. The laminated electrophotographic photoreceptor according to claim 1, wherein the charge transport layer comprises a hole transport material and a binder. 6. The laminated electrophotographic photoconductor according to claim 5, wherein the hole transporting substance is a hydrazone compound. 7. The laminated electrophotographic photoconductor according to claim 6, wherein the hydrazone compound is a hydrazone compound having an indoline ring. 8. The laminated electrophotographic photoconductor according to claim 6, wherein the hydrazone compound is a hydrazone compound having a quinoline ring. 9. The laminated electrophotographic photoreceptor according to claim 5, wherein the hole transporting substance is an aromatic amine compound. 10. A hydrazone compound having an indoline ring is represented by the general formula: (In the formula, R ₁ represents an alkyl group, an aralkyl group or an aryl group which may have a substituent, and R ₂ and R ₃ each independently have a hydrogen atom, a halogen atom or a substituent. R ₄ represents an alkyl group, an aralkyl group or an aryl group, R ₄ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group or an aralkyl group, and R ₅ and R ₆ each independently have a substituent. Represents an alkyl group, an aralkyl group or an aryl group which may be represented by R
₅ and R ₆ may be integrated with each other to form a ring. The laminated type electrophotographic photoreceptor according to claim 7, which is a hydrazone compound represented by 11. A hydrazone compound having a quinoline ring has the general formula (In the formula, B represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom or a substituent. Which represents an alkyl group, an aralkyl group or an aryl group which may have a hydrazone type compound. 12. The aromatic amine compound has the general formula (Wherein Ar ₁ , Ar ₂ and Ar ₃ represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent), and the laminated electron according to claim 9. Photoreceptor for photography.