JPH117143A - Laminated electrophotographic photoreceptor and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoreceptor having high sensitivity for semiconductor laser light, excellent repetition stability for sensitivity and electrification property, and excellent long-term stability in a dark environment. SOLUTION: This photoreceptor 1 is obtd. by successively depositing at least a charge producing layer 3 and a charge transfer layer 4 in this order on a conductive base body 2. The charge producing layer 3 is an oxotitanium phthalocyanine vapor deposition film. The oxotitanium phthalocyanine vapor deposition film is subjected to exposure treatment to a mixture vapor of at least an aromatic org. solvent and water or a mixture vapor of at least a chlorinated aliphatic hydrocarbon and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated electrophotographic photosensitive member used in an electrophotographic apparatus and a method of manufacturing the same, and more particularly, to a laminated electrophotographic photosensitive member using an oxotitanium phthalocyanine deposited film as a charge generating layer. The present invention relates to a photosensitive member for use and a method for manufacturing the same.

[0002]

2. Description of the Related Art An electrophotographic apparatus is excellent in high-speed recording and low-noise properties, and has advantages such as being capable of recording with high image quality and recording on plain paper. Therefore, not only as a copying machine, but also as a printer and a facsimile, etc., it is becoming very popular. And
Especially in fields such as printers and facsimile machines,
Since the usage pattern is shifting from office use to personal use, further miniaturization and cost reduction, as well as maintenance-free, are required, and image processing that can obtain higher resolution and higher quality images There is a demand for the adoption of technology. Further, as a photoreceptor used in an electrophotographic apparatus, an organic photoreceptor having advantages such as easy film formation, low cost and no pollution, that is, an organic photoreceptor configured to contain an organic photoconductive material is used. High sensitivity in the long wavelength region suitable for laser beam printers and facsimile machines that use semiconductor lasers as an exposure light source (hereinafter referred to as sensitivity).
The development of organic photoreceptors having phenomena is remarkable.

[0003] That is, most of organic photoreceptors that have been put to practical use have a laminated structure in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are provided on a conductive support. This type of laminated electrophotographic photoreceptor has a thin-film charge generation layer formed on a conductive support (not shown). In addition to forming a relatively thick charge transport layer on the
A photosensitive layer is constituted by these two layers. In this case, the charge generation layer is a carrier.
The charge transport layer has a function of transporting carriers and a function of maintaining a charging potential of the photoconductor, and a function of maintaining mechanical strength of the photoconductor. is there.

Further, in recent years, phthalocyanines having high sensitivity in a long wavelength region, which is an oscillation wavelength region of a semiconductor laser, have been attracting attention as a charge generating substance. Among these pigments, phthalocyanine using oxotitanium phthalocyanine has been attracting attention. Generation layers have been put to practical use. A method of forming a charge generation layer while using oxotitanium phthalocyanine as a charge generation agent is roughly classified into 2 methods.
In the first method, a coating in which a certain kind of oxotitanium phthalocyanine of a certain crystal type is dispersed in a solvent together with a resin binder is used, and a coating having a thin film thickness of about 0.1 μm to 0.5 μm is used. The film is formed as a charge generation layer by coating. Further, in the second method, after depositing oxotitanium phthalocyanine on the conductive support, the resulting oxotitanium phthalocyanine deposited film may be brought into contact with the vapor of a soluble solvent to form a charge generation layer. Is being done.

[0005] Japanese Patent Application Laid-Open No. Sho 59-166959 proposes a specific example of the second method. That is, the oxotitanium phthalocyanine deposited film immediately after the deposition has a crystal form in which the maximum absorption peak wavelength of the light absorption spectrum is 720 nm, but when the oxotitanium phthalocyanine film is exposed to a vapor of a soluble solvent such as tetrahydrofuran, the exposure treatment is performed. Crystal form having a maximum absorption peak wavelength of 830 nm in a light absorption spectrum
(β-type), and when the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment with tetrahydrofuran vapor is used as a charge generation layer, it can form an organic photoreceptor that is advantageous for semiconductor laser light. Is the way. In this publication, the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment with tetrahydrofuran vapor has a Bragg angle (2θ) of 7.5 °, 12.6 °, 13.0 °, 25.4 ° in the X-ray diffraction spectrum. , 2
It is also shown that it has strong diffraction peaks at 6.2 ° and 28.6 °, respectively.

[0006]

As described above, when forming a charge generation layer using oxotitanium phthalocyanine, a thin coating film is formed by using a coating material in which oxotitanium phthalocyanine is dispersed in advance. First
And a second method in which an oxotitanium phthalocyanine vapor-deposited film is formed and then subjected to exposure treatment. Of these two methods, the second method is more advantageous than the first method in that a thin film having a uniform concentration can be easily formed, and a film having excellent stability can be obtained. It is supposed to be.

However, Japanese Patent Application Laid-Open No. 59-166959 discloses
In the laminated electrophotographic photoreceptor obtained by employing the method disclosed in Japanese Patent Application Laid-Open Publication No. H10-209, the light absorption wavelength was shifted to a longer wavelength region by exposing the oxotitanium phthalocyanine vapor-deposited film to a vapor of a soluble solvent. In addition, since the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment is used as the charge generation layer, the charging characteristics such as the sensitivity and charge potential of the charge generation layer (hereinafter, chargeability ), And in particular, the repetition stability such as sensitivity and chargeability will be reduced. Also, if the laminated electrophotographic photosensitive member constructed according to the conventional procedure is left in the dark, there has been a problem that the charging property is reduced.

The present invention has been made in view of these disadvantages, and has high sensitivity to semiconductor laser light, and has excellent repetition stability such as sensitivity and chargeability. An object of the present invention is to provide a laminated electrophotographic photoconductor having excellent long-term stability in the dark and a method for producing the same.

[0009]

According to a first aspect of the present invention, there is provided a laminated electrophotographic photoreceptor comprising at least a charge generation layer and a charge transport layer laminated on a conductive support in this order. The charge generation layer is an oxotitanium phthalocyanine vapor-deposited film, and the oxotitanium phthalocyanine vapor-deposited film is subjected to exposure treatment with a mixed vapor containing at least an aromatic organic solvent and water. In the laminated electrophotographic photoreceptor according to the first aspect, the oxotitanium phthalocyanine vapor-deposited film exposed to the mixed vapor containing at least the aromatic organic solvent and water has an α-type and a β-type. Intermediate crystalline form (the maximum peak wavelength of the light absorption spectrum is 780 ± 10
It has a high sensitivity to semiconductor laser light, and has a high trapping and recombination of carriers. This means that the charge generation layer having less generation is provided. As a result, a photosensitive layer having excellent sensitivity and chargeability, excellent repeatability such as sensitivity and chargeability, and excellent long-term stability in the dark can be obtained.

[0010] The laminated electrophotographic photoreceptor according to the second aspect of the present invention is characterized in that the aromatic organic solvent is chlorobenzene, toluene, or a mixture thereof. And when these aromatic organic solvents are used, the disorder of the crystal orientation in the oxotitanium phthalocyanine vapor-deposited film is further reduced, so that the sensitivity and chargeability, and the repetition stability thereof are significantly improved. It will be.

According to a third aspect of the present invention, there is provided a photoreceptor for electrophotography, wherein at least a charge generation layer and a charge transport layer are laminated on a conductive support in this order, and the charge generation layer is oxo. A titanium phthalocyanine deposited film,
This oxotitanium phthalocyanine vapor-deposited film is characterized in that it is exposed to at least a mixed vapor of chlorinated aliphatic hydrocarbon and water. Also, this laminated electrophotographic photoreceptor has excellent sensitivity and chargeability, excellent repeatability such as sensitivity and chargeability, and also excellent long-term stability in the dark. The resulting photosensitive layer is obtained.

[0012] The laminated electrophotographic photoreceptor according to claim 4 of the present invention is characterized in that the chlorinated aliphatic hydrocarbon is chloroform, dichloroethane, or a mixture thereof. When these chlorinated aliphatic hydrocarbons are used, the sensitivity and chargeability as a result of the disorder of the crystal orientation in the oxotitanium phthalocyanine vapor-deposited film being further reduced, and the repetition stability thereof are significantly improved. Will do.

[0013] The laminated electrophotographic photoreceptor according to claim 5 of the present invention is characterized in that the maximum peak wavelength of the light absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is 780 ± 10 nm. .
In such a configuration, the charge generation layer has excellent sensitivity to the semiconductor laser light and has a low occurrence of carrier trapping and recombination.
It has excellent sensitivity and chargeability, and also has excellent repeatability such as sensitivity and chargeability.

In the laminated electrophotographic photoreceptor according to the present invention, the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer has a thickness of 0.03 μm to 0.5 μm.
It is characterized by being within the range up to. When such a configuration is employed, a sufficient carrier generation amount can be obtained, and the dark decay can be reduced and the charged potential can be maintained high. As a result, good sensitivity can be obtained. , And the repetition stability such as sensitivity and charging property are further improved.

According to a seventh aspect of the present invention, there is provided a laminated electrophotographic photoreceptor wherein an oxotitanium phthalocyanine vapor-deposited film as a charge generation layer is formed using oxotitanium phthalocyanine obtained by acid paste treatment. It is characterized by being. When such a treatment is performed, the oxotitanium phthalocyanine molecule is once decomposed by sulfuric acid, so that impurities contained in the pigment particles, that is, impurities that adversely affect the electrical characteristics are easily removed. As a result, excellent sensitivity and chargeability can be obtained, and a photosensitive layer having excellent long-term stability in the dark can be obtained.

[0018] In the laminated electrophotographic photoreceptor according to the present invention, the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is formed by using oxotitanium phthalocyanine obtained by subjecting to an acid paste treatment and sublimation purification. It is characterized in that it is. Depending on the treatment at this time, the electrical characteristics of the oxotitanium phthalocyanine vapor-deposited film are greatly improved, and the charge retention characteristics and sensitivity are further improved.As a result, image noise called black spots is almost recognized in actual image formation. It is possible to improve the image quality to an extent that is not so large. In addition,
This is considered to be because the content of impurities in the pigment becomes extremely small, and the amount of impurities taken into the deposited film in the process of forming the deposited film of oxotitanium phthalocyanine is considered to be extremely small. .

According to a ninth aspect of the present invention, the charge transport layer is formed by using a transport layer-forming coating liquid, and the transport layer-forming coating liquid comprises a charge transport agent and a charge transport agent. It is characterized by being obtained by dissolving a resin binder with toluene or chloroform. The charge transport layer thus formed does not change the crystal form of the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment, and has high transparency.As a result, the sensitivity of the photosensitive layer is reduced. It will be even better.

According to a tenth aspect of the present invention, in the laminated electrophotographic photoreceptor, the charge transporting agent comprises 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis ( p-diethylaminophenyl)
It is a mixture with -4,4-diphenyl-1,3-butadiene. When this type of charge transport agent is used, a photosensitive layer having excellent ozone resistance can be obtained.

[0020] In the laminated electrophotographic photoreceptor according to the present invention, the charge transporting agent is 4-N, N-diphenylamino-α-phenylstilbene. When this kind of charge transport agent is used, a photosensitive layer having excellent sensitivity and chargeability, excellent repetition stability thereof, and excellent ozone resistance can be obtained. become.

[0020] In the method of manufacturing a laminated electrophotographic photoreceptor according to the present invention, at least a charge generation layer and a charge transport layer are laminated in this order on a conductive support. It is a method of manufacturing a photoreceptor, the step of forming a charge generation layer, the step of depositing oxotitanium phthalocyanine on a conductive support, the obtained oxotitanium phthalocyanine deposited film of an aromatic organic solvent and water Exposing with a mixed vapor. By adopting such a method, a photosensitive layer having excellent sensitivity and chargeability, excellent repeatability such as sensitivity and chargeability, and excellent long-term stability in the dark. Can be manufactured rationally and stably.

According to a thirteenth aspect of the present invention, in the method of manufacturing a laminated electrophotographic photoreceptor, at least a charge generation layer and a charge transport layer are laminated on a conductive support in this order. It is a method of manufacturing a photoreceptor, the step of forming a charge generation layer, the step of depositing oxotitanium phthalocyanine on a conductive support, the resulting oxotitanium phthalocyanine deposited film chlorinated aliphatic hydrocarbons and water And performing an exposure treatment with a mixed vapor of the above. Also, according to this manufacturing method, a photosensitive layer having excellent sensitivity and chargeability, excellent repeatability such as sensitivity and chargeability, and also excellent in long-term stability in darkness is rationalized. In this way, it is possible to manufacture the product stably and stably.

According to a fourteenth aspect of the present invention, in the method of manufacturing a laminated electrophotographic photoreceptor, the exposure time of the oxotitanium phthalocyanine vapor-deposited film is in the range of 30 seconds to 3 hours. I have. Then, when this manufacturing method is adopted, the entire oxotitanium phthalocyanine vapor-deposited film formed over the entire area of the conductive support, even if the conductive support is in the form of a long drum, has a preferable crystal form, that is, It can be modified to a crystal form having a maximum peak wavelength of 780 ± 10 nm in the light absorption spectrum.

[0023] According to a fifteenth aspect of the present invention, in the method of manufacturing a laminated electrophotographic photoreceptor, the step before forming the charge generation layer includes
The method includes a step of subjecting oxotitanium phthalocyanine to acid paste treatment. And, in this production method, since the oxotitanium phthalocyanine molecule is once decomposed by sulfuric acid, it is possible to easily remove impurities that have an adverse effect on the electric characteristics.
A photosensitive layer having excellent sensitivity and chargeability and having excellent long-term stability in the dark can be produced.

[0024] In the method for manufacturing a laminated electrophotographic photoreceptor according to claim 16 of the present invention, the step before forming the charge generation layer includes the following steps:
It is characterized by comprising a step of subjecting oxotitanium phthalocyanine to acid paste treatment and then sublimation purification. According to this manufacturing method, the electric characteristics of the oxotitanium phthalocyanine vapor-deposited film are greatly improved, and as a result, the charge retention characteristics and sensitivity of the photosensitive layer are further improved, and to the extent that image noise called a black spot is hardly recognized. The image quality at the time of actual image formation is improved.

[0025] In the method of manufacturing a laminated electrophotographic photoreceptor according to claim 17 of the present invention, the step of forming the charge transport layer comprises forming the charge transport layer by dissolving a charge transport agent and a resin binder with toluene or chloroform. The method is characterized by including a step of dip-coating a coating liquid on an oxotitanium phthalocyanine vapor-deposited film as a charge generation layer. And when such a manufacturing method is adopted, a highly transparent charge transport layer is provided, and a photosensitive layer with further improved sensitivity,
That is, it is possible to efficiently manufacture a photosensitive layer having a high initial charging potential and having less charging unevenness.

[0026]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing the structure of the laminated electrophotographic photosensitive member according to the present embodiment.
In the figure, reference numeral 1 indicates a laminated electrophotographic photosensitive member. In the laminated electrophotographic photoreceptor 1, a thin charge generation layer 3 is formed on a conductive support 2, and a relatively thick charge transport layer is formed on the charge generation layer 3. 4
Are formed, and the charge-generating layer 3 and the charge-transporting layer 4 constitute an organic photosensitive layer 5. That is, the conductive support 2 included in the laminated electrophotographic photoreceptor 1 is made of a substrate made of a conductive material known per se, for example, a metal material such as aluminum or a conductive plastic (phenol). A substrate made of an insulating resin such as resin and conductive particles such as carbon dispersed), or glass coated with a conductive material such as aluminum iodide, copper iodide, chromium oxide or tin oxide The substrate at this time has a shape such as a drum shape (pipe shape), a plate shape, a belt shape, or the like, that is, a shape that is not particularly limited.

The charge generation layer 3 is an oxotitanium phthalocyanine vapor-deposited film obtained by vapor-depositing oxotitanium phthalocyanine on the conductive support 2 in a vacuum. The film is formed by using oxotitanium phthalocyanine subjected to acid paste treatment. In the case of such a pigment, the oxotitanium phthalocyanine molecule is once decomposed by sulfuric acid at the time of acid paste treatment, and impurities embraced in the pigment particles, that is, impurities that adversely affect the electrical characteristics are previously removed. Since it has been removed, excellent sensitivity and chargeability can be obtained, and the long-term stability in darkness is also excellent.

In this case, it is more preferable to use not only acid paste treatment but also oxotitanium phthalocyanine which has been subjected to acid paste treatment and purified by sublimation. When such a pigment is used, most of the impurities are removed by a two-step treatment of acid paste treatment and sublimation purification, and the pigment is extremely pure. Therefore, the electrical characteristics of the oxotitanium phthalocyanine vapor-deposited film are reduced. Is greatly improved, and the charge retention characteristics and sensitivity are further improved. That is, in the process of forming the charge generation layer 3 in manufacturing the laminated electrophotographic photoreceptor 1 according to the present embodiment, the step of applying oxotitanium phthalocyanine to the acid paste or the step of applying oxotitanium phthalocyanine to the acid paste is performed. And then a step of sublimation purification.

Further, the oxotitanium phthalocyanine vapor-deposited film, which is the charge generation layer 3 formed as described above, is a mixed vapor containing at least an aromatic organic solvent and water, or at least a chlorinated aliphatic. Exposure treatment with a mixed vapor containing a hydrocarbon and water results in a maximum peak wavelength of a light absorption spectrum of 78.
The crystal was converted into a crystal form showing 0 ± 10 nm. Then, it is estimated that the oxotitanium phthalocyanine when such an exposure treatment is performed has a crystal in a crystal form positioned between an α-type crystal and a β-type crystal, and the mixed vapor as described above. The charge generation layer 3 made of an oxotitanium phthalocyanine vapor-deposited film subjected to the exposure treatment described above has a small disorder in the crystal orientation and causes less occurrence of carrier traps and recombination.
That is, the step of forming the charge generation layer 3 at this time is as follows:
A step of depositing oxotitanium phthalocyanine on the conductive support 2 and a step of depositing the obtained oxotitanium phthalocyanine deposited film on a mixed vapor containing at least an aromatic organic solvent and water, or at least a chlorinated aliphatic hydrocarbon. And performing an exposure treatment with a mixed vapor containing water.

The aromatic organic solvent used for the exposure treatment of the oxotitanium phthalocyanine vapor-deposited film generally has 6 to 8 carbon atoms, and specific examples thereof include benzene, toluene, xylene, and chlorobenzene. ,
Alternatively, a mixture consisting of two or more of these can be mentioned. In particular, it is preferable to use chlorobenzene or toluene, or a mixture of these from the viewpoint of stabilizing the crystal conversion of oxotitanium phthalocyanine. Become. The mixed vapor has a mixing ratio of aromatic organic solvent and water (aromatic organic solvent: water) of 5: 1 to 50: 1, preferably 10:50.
It is produced using a mixed solvent in the range of 1 to 20: 1.
A required amount of the mixed solvent within the temperature range of 25 ° C. to 25 ° C. is stored in an appropriate container, and a mixed vapor corresponding to the vapor pressure corresponding to the temperature of each solvent contained in the mixed solvent is generated. Is done.

On the other hand, as the chlorinated aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon having 2 or less carbon atoms is used, and specific examples include dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane and the like. And one or more of these are used after being mixed. In particular, it is preferable to use chloroform, dichloroethane, or a mixture thereof, since the crystal conversion of oxotitanium phthalocyanine is stabilized. In addition,
The mixed steam has a mixing ratio of chlorinated aliphatic hydrocarbon to water (chlorinated aliphatic hydrocarbon: water) of 5: 1 to 50:50.
1, preferably using a mixed solvent in the range of 10: 1 to 20: 1, and adding the mixed solvent in the temperature range of 15 ° C. to 25 ° C. to a suitable container in an appropriate amount. When stored, mixed vapor corresponding to the vapor pressure corresponding to the temperature of each solvent constituting the mixed solvent is generated.

Further, the thickness of the charge generation layer 3 comprising an oxotitanium phthalocyanine vapor-deposited film is 0.03 μm.
m to 0.5 μm, preferably 0.1 μm
To about 0.2 μm. It should be noted that regulating the film thickness of the oxotitanium phthalocyanine vapor-deposited film in this way is that if the film thickness is too small, the amount of generated carriers is reduced, and it tends to be difficult to obtain sufficient sensitivity, while the charge If the thickness of the generating layer 3 is too large, the dark decay increases, the charging potential decreases, and the charging property and the repetition stability of sensitivity tend to decrease. When the thickness of the charge generation layer 3 is set in the range of 0.03 μm to 0.5 μm, a sufficient amount of carriers can be obtained, and dark decay can be sufficiently reduced. .

The exposure time of the oxotitanium phthalocyanine vapor-deposited film with a mixed vapor containing an aromatic organic solvent and water or a mixed vapor containing a chlorinated aliphatic hydrocarbon and water is from 30 seconds to 3 hours. Generally, it is within the range of 5 minutes to 6 minutes.
It is about 0 minutes. The reason why the exposure time is regulated in this way is that if the exposure time is shorter than 30 seconds, the conductive support 2 may be in the form of a long drum having a length of 300 mm or more. It is difficult to sufficiently and simultaneously carry out the crystal conversion of the oxotitanium phthalocyanine vapor-deposited film formed over the entire region of the body 2, and when the exposure time exceeds 3 hours, the maximum peak wavelength of the light absorption spectrum is reduced. This is because there is a possibility that the crystal conversion to a crystal form other than the crystal form showing 780 ± 10 nm may be performed.

Next, the charge transport layer 4 which is provided in the multi-layer electrophotographic photoreceptor 1 according to the present embodiment and which constitutes the organic photosensitive layer 5 after being integrated with the charge generation layer 3 will be described. . First, the charge transport layer 4 is formed by using a coating liquid for forming a transport layer, and the transport layer is formed on the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 by employing a conventionally known coating method. It is formed by dip coating a forming coating solution and then drying the coating film. The coating liquid for forming a transport layer is a solution in which a charge transport agent and a resin binder are dissolved with an appropriate solvent.As the charge transport agent in this case, oxazole, oxadiazole, a heterocyclic compound such as pyrazoline, or And various derivative substances such as hydrazone compounds, butadiene compounds, stilbene compounds, and these compounds.

Further, specific examples of the charge transport agent include 2
-Methyl-4-dibenzylaminobenzaldehyde-
N, N-diphenylhydrazone or 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3
-Butadiene, 4-N, N-diphenylamino-α-phenylstilbene, 4- {N- (p-methoxyphenyl)
—N-phenylamino} -α-phenylstilbene and the like. And 2-methyl-4 of these
When a mixture of -dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene is used, 4-N, N- When diphenylamino-α-phenylstilbene is used, it is possible to form the organic photosensitive layer 5 having excellent sensitivity and less deterioration by ozone.

It should be noted that 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl) -4,4-
When a mixture with diphenyl-1,3-butadiene is used, the mixing ratio is 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone to 1,1-bis (p-diethylaminophenyl) -4. , 4
The weight ratio of diphenyl-1,3-butadiene is 99: 1
It is preferable to adjust so as to fall within a range of 30:70. That is, in this case, if the amount of 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone is too large, the sensitivity tends to decrease, and 1,1-bis (p-diethylaminophenyl)-
If the amount of 4,4-diphenyl-1,3-butadiene is too large, the ozone resistance tends to decrease. Therefore, by setting the compounding ratio of both to the above range, good sensitivity and good ozone resistance can be obtained. This is because it is possible to obtain the property.

Further, examples of the resin binder for forming the coating liquid for forming the transport layer include resins such as polyester, polycarbonate, polysulfone, and polymethyl methacrylate, while the solvents include ketones such as methyl ethyl ketone and tetrahydrofuran. And various organic solvents such as chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, and chloroform; and aromatic hydrocarbons such as benzene and toluene. And among these organic solvents, chloroform or toluene is the most preferred solvent,
When these are used, the charge generation layer 3 after the exposure treatment is used.
As a result, the charge transport layer 4 having high transparency can be formed without changing the crystal form of the oxotitanium phthalocyanine vapor-deposited film, thereby obtaining the organic photosensitive layer 5 having excellent sensitivity. The composition of the transport layer forming coating liquid is not limited, and the weight ratio of the charge transport agent to the resin binder (charge transport agent: resin binder) is 80:20 to 2
Generally, the ratio is within the range of 0:80, but the charge transport agent and the resin binder have a total solid content concentration of 1%.
It is to be dissolved in a solvent after being adjusted to be 0 to 40% by weight.

By the way, the method of applying the transport layer forming coating liquid is not limited, but a coating film is formed by immersing the object to be coated in a coating liquid (coating liquid) and pulling it up. In general, a so-called dip coating method is used. When such a method is used, a relatively thick film having a uniform thickness can be formed easily and in a short time. Becomes possible. The formed charge transport layer 4 has a thickness of 5 μm to 40 μm, preferably 15 μm to 25 μm, and when the thickness of the charge transport layer 4 is set within the above range. Means that the initial charging potential of the organic photosensitive layer 5 can be set sufficiently high. That is, in the step of forming the charge transport layer 4 according to the present embodiment, the transport layer forming coating solution obtained by dissolving the charge transport agent and the resin binder in toluene or chloroform is coated with the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3. It includes a step of dip coating on top.

[0040]

EXAMPLES Hereinafter, specific examples and comparative examples of the present embodiment will be described.

(Example 1) In synthesizing oxotitanium phthalocyanine, the following procedure is employed.
First, 1-chloronaphthalene stored in a three-necked flask
(770 ml) of 1,3-diiminoisoindoline
13 g was added and suspended, and while stirring, 75 g of tetra-n-butyl titanate was added.
Heat for 4 hours in a nitrogen atmosphere at 5 ° C.
The mixture was allowed to cool to ℃. Then, the reaction product was separated by filtration, washed with 1-chloronaphthalene (100 ml) heated to 100 ° C., and then sufficiently washed with ethanol (1000 ml). Then, while using dimethylformamide (500 ml),
The hot-suspension washing for 1 hour at 0 ° C. is repeated three times, and the hot-suspension washing for 1 hour at 60 ° C. is repeated twice using ethanol (500 ml), and then dried under vacuum at a temperature of 50 ° C. I did that. The yield of the pigment thus obtained, that is, oxotitanium phthalocyanine, was 81 g.

Also, concentrated sulfuric acid (97%, d = 1.84) 30
0 g was placed in an Erlenmeyer flask and stirred with a stirrer while cooling with an ice-water bath. Then, 15 g of oxotitanium phthalocyanine obtained according to the above procedure was added over about 45 minutes, and then stirred for 1.5 hours. Went on to continue. Further, after suction filtration was performed using a glass filter, the obtained filtrate was poured little by little into 51 g of ice water with stirring with a glass rod to precipitate a pigment. Subsequently, the obtained precipitate was filtered off with a Buchner funnel under suction, and the filtrate was thoroughly washed with distilled water until the filtrate became acidic to neutral. Vacuum drying was performed underneath. And at a temperature of 50 ° C.
The purified product obtained by performing vacuum drying for 10 hours at a temperature of 100 ° C. for 10 hours, that is, the yield of oxotitanium phthalocyanine subjected to acid paste treatment was 75 g.

Next, a specific manufacturing procedure of the laminated electrophotographic photosensitive member 1 will be described. First, the oxotitaniumphthalocyanine obtained according to the procedure described above, 10 ^-5-to
Under vacuum of rr to 10 ⁻⁶ torr, 0.1 μm on an aluminum plate as a substrate having a thickness of 0.5 mm.
Was deposited at a thickness of. Then, 10 ml of a mixed solvent of chlorobenzene and water at 20 ° C. (the mixing ratio of chlorobenzene and water was 20: 1) was stored in 10 ml.
A beaker of 00 ml was prepared, and the substrate on which the oxotitanium phthalocyanine vapor-deposited film was formed was placed in a beaker and sealed with a lid, so that oxotitanium phthalocyanine was vapor-deposited in a mixed vapor containing chlorobenzene and water. The membrane was left for 30 minutes. Then, as a result of the exposure treatment using the mixed vapor, as shown in FIG. 2, the maximum peak wavelength region of the light absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film shifted to the longer wavelength side. Here, FIG. 2 (a)
Shows a light absorption spectrum immediately after the formation of the oxotitanium phthalocyanine vapor-deposited film, and it can be seen that the maximum peak wavelength is around 721 nm. On the other hand, FIG.
Shows the light absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment with the mixed vapor containing chlorobenzene and water, and it is clear that the maximum peak wavelength after such exposure treatment is around 778 nm. ing.

Further, 4-N, N-diphenylamino-α is deposited on the oxotitanium phthalocyanine vapor-deposited film, which is the charge generation layer 3 formed according to the above procedure.
20 parts by weight of phenylstilbene and 20 parts by weight of a polycarbonate resin (manufactured by Mitsubishi Gas Chemical Industry Co., Ltd., trade name Iupilon Z-300) were dissolved in 100 parts by weight of toluene to prepare a transport layer forming coating liquid. After being applied by dip coating, the charge transport layer 4 having a thickness of 20 μm after drying was formed, thereby completing the laminated electrophotographic photoreceptor 1. Subsequently, the electrostatic properties of the completed laminated electrophotographic photoreceptor 1 were evaluated by using an electrostatic copying paper tester (Model EPA-8100 manufactured by Kawaguchi Electric Works, Ltd.). The results shown in Table 1 were obtained. was gotten.

In this evaluation test, the corona current was-
The initial charging potential when the multilayer electrophotographic photosensitive member 1 is negatively charged in a dark place by corona discharge at an applied voltage set to 30 μA is Vmax (V), and the surface potential after one second of dark decay is V0. (V) After measuring the charge retention for one second in dark decay as DD (%), the maximum peak wavelength was 800
the surface potential when irradiated with monochromatic light having an energy of 2.1 μJ / cm ² · s for 4 seconds, which is 秒 間 V0 nm.
And E1 / 5 (μJ / cm ² ), respectively, and the surface potential 4 seconds after the exposure was measured as a residual potential VR (V). ing. In this evaluation test, the repetition stability of electrostatic characteristics (sensitivity and charging characteristics) when the series of measurement operations described above was repeated 1,000 times was also evaluated. The potential VR (V) is to be a residual potential two seconds after exposure.

[0046]

[Table 1]

Example 2 In Example 2, a mixed vapor containing toluene and water was used instead of a mixed vapor containing chlorobenzene and water. To obtain such a mixed vapor, A mixed solvent consisting of toluene and water (the mixing ratio of toluene and water is 10: 1) is used. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. As shown in Table 1, Results were obtained. FIG. 3 is an explanatory view showing a change state of a light absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after an exposure treatment when a mixed vapor containing toluene and water is used. According to FIG. It is clear that the maximum peak wavelength of the spectrum is around 780 nm.

Example 3 In Example 3, a mixed vapor containing chloroform and water was used instead of a mixed vapor containing chlorobenzene and water. To obtain such a mixed vapor, A mixed solvent composed of chloroform and water (the mixing ratio of chloroform and water is 10: 1) is used. Then, the laminated electrophotographic photoconductor 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photoconductor 1 were evaluated.
The results as shown in Table 1 were obtained. FIG. 4 is an explanatory view showing a change state of the light absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment when using the mixed vapor containing chloroform and water. According to FIG. The maximum peak wavelength of the spectrum is 789n
m.

Example 4 In Example 4, a mixed vapor containing dichloroethane and water was used instead of a mixed vapor containing chlorobenzene and water. To obtain such a mixed vapor, A mixed solvent consisting of dichloroethane and water (mixing ratio of dichloroethane and water is 10: 1) is used. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. As shown in Table 1, Results were obtained. FIG. 5 is an explanatory view showing a change state of a light absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after an exposure treatment when a mixed vapor containing dichloroethane and water is used. According to FIG. It can be seen that the maximum peak wavelength of the spectrum is around 786 nm.

Example 5 In Example 1, an oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 was formed by using oxotitanium phthalocyanine obtained by acid paste treatment. An oxotitanium phthalocyanine vapor-deposited film is formed by using oxotitanium phthalocyanine obtained by sublimation purification after acid paste treatment. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

Incidentally, the oxotitanium phthalocyanine at this time is to be purified by sublimation according to the following procedure. First, about 10 g of oxotitanium phthalocyanine weighed was 10 cm × 5 cm.
The quartz boat was spread on a quartz boat having a size of about 10 cm, and the quartz boat was placed in a quartz pipe having a diameter of about 8 cm. Then, the inside of the quartz pipe was evacuated by a vacuum pump until the internal pressure became about 1 Pascal. Subsequently, the quartz boat placed in the quartz tube was placed in an electric furnace while being positioned at the center of heating, and heated at a temperature of about 450 ° C. for 30 hours while evacuating with a vacuum pump. Then, after cooling down to room temperature, oxotitanium phthalocyanine precipitated on the inner surface of the quartz tube near where the quartz boat was arranged was collected, and the yield of oxotitanium phthalocyanine obtained after sublimation purification was about 7 g.
Met.

Example 6 The transport layer forming coating solution in Example 1 was composed of 20 parts by weight of 4-N, N-diphenylamino-α-phenylstilbene and 2 parts by weight of a polycarbonate resin.
0 part by weight was dissolved in 100 parts by weight of toluene, but instead of such a coating liquid for forming a transport layer, in Example 6, 2-methyl-4-dibenzylaminobenzaldehyde-N, 18 parts by weight of N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl)-
The charge transport layer 4 is formed by using a transport layer-forming coating solution using 2 parts by weight of 4,4-diphenyl-1,3-butadiene as a charge transport agent and chloroform as a solvent. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten. Example 6
In this method, an oxotitanium phthalocyanine vapor-deposited layer is subjected to an exposure treatment using a mixed vapor containing chlorobenzene and water.

Example 7 Example 7 differs from Example 6 in which a mixed vapor containing chlorobenzene and water is used.
The exposure treatment is performed by using a mixed vapor containing toluene and water. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 6, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

(Example 8) The coating liquid for forming a transport layer in Example 8 was prepared using chloroform in place of toluene in Example 1, and the other conditions were the same as in Example 1. I have. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

(Example 9) In place of 4-N, N-diphenylamino-α-phenylstilbene in preparing the transport layer forming coating liquid of Example 1, 4- {N- (p-methoxyphenyl) Example 9 prepared a transport layer-forming coating liquid by using -N-phenylamino} -α-phenylstilbene. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten. In the ninth embodiment, the oxotitanium phthalocyanine vapor-deposited layer is exposed by using a mixed vapor containing chlorobenzene and water.

(Embodiment 10) The mixed steam in Embodiment 6
That is, the tenth embodiment uses a mixed vapor containing chloroform and water instead of the mixed vapor containing chlorobenzene and water. Then, according to the same procedure as in Example 6, the laminated electrophotographic photosensitive member 1 was completed, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. Such a result was obtained.

(Example 11) In Example 11, a mixed vapor containing dichloroethane and water was used in place of the mixed vapor in Example 6, and the laminated electrophotography was performed in the same procedure as in Example 6. The photoreceptor 1 was completed, and the electrostatic properties of the completed laminated electrophotographic photoreceptor 1 were evaluated. The results shown in Table 1 were obtained.

(Example 12) In Example 6, an oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 is formed by using oxotitanium phthalocyanine obtained by acid paste treatment.
In Example 12, an oxotitanium phthalocyanine vapor-deposited film is formed using oxotitanium phthalocyanine obtained by sublimation purification after acid paste treatment. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 6, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

(Example 13) The coating liquid for forming a transport layer in Example 13 was the same as Example 1 except that dioxane was used instead of toluene in Example 1. . Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

(Example 14) The coating liquid for forming a transport layer in Example 14 was prepared by using tetrahydrofuran instead of toluene in Example 1, and the other conditions were the same as those in Example 1. I have. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 1, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

(Example 15) The coating liquid for forming a transport layer in Example 6 was composed of 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-
Although bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene was dissolved in chloroform, in Example 15, tetrahydrofuran was used as a solvent instead of chloroform. Have been done. Then, the laminated electrophotographic photosensitive member 1 was completed according to the same procedure as in Example 6, and the electrostatic characteristics of the completed laminated electrophotographic photosensitive member 1 were evaluated. The results shown in Table 1 were obtained. was gotten.

Example 16 4-Diethylaminobenzaldehyde-N, N-diphenylhydrazone was used instead of 4-N, N-diphenylamino-α-phenylstilbene in preparing the coating solution for forming a transport layer in Example 8. In Example 16, a coating liquid for forming a transport layer was prepared by using Then, the laminated electrophotographic photoconductor 1 was completed according to the same procedure as in Example 8, and the electrostatic characteristics of the completed laminated electrophotographic photoconductor 1 were evaluated. The results shown in Table 1 were obtained. was gotten. In this embodiment 16,
Exposure treatment is performed on an oxotitanium phthalocyanine vapor-deposited layer with a mixed vapor containing chloroform and water.

(Example 17) The coating liquid for forming a transport layer in Example 17 was the same as Example 16 except that toluene was used instead of chloroform in Example 16. Thus, the multilayer electrophotographic photoconductor 1 was completed according to the same procedure as in Example 16, and the electrostatic characteristics of the completed multilayer electrophotographic photoconductor 1 were evaluated.
The results as shown in Table 1 were obtained.

(Embodiment 18) Some of the laminated electrophotographic photoreceptors 1 manufactured according to the same procedures as those described in each of Embodiments 1 to 17 described above have a long-term stability in a dark place. In order to evaluate the electrostatic properties, after measuring the initial electrostatic characteristics and leaving it in a dark place for three months, the electrostatic characteristics were measured again, and the results shown in Table 2 were obtained. Have been.

[0065]

[Table 2]

Comparative Example 1 In Comparative Example 1, the charge generation layer 3 was formed using oxotitanium phthalocyanine synthesized without acid paste treatment, and the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 was formed. Was exposed to a mixed vapor containing chlorobenzene and water, and a laminated electrophotographic photoreceptor 1 was completed in the same procedure as in Example 1. When the electrostatic characteristics of the completed laminated electrophotographic photoreceptor 1 were evaluated, the results shown in Tables 1 and 2 were obtained.

(Comparative Example 2) An oxotitanium phthalocyanine vapor-deposited film formed according to the same procedure as in Comparative Example 1 was exposed to acetone vapor for 30 minutes, and the other procedures were the same as in Example 1. Thus, a laminated electrophotographic photoreceptor 1 was completed. When the electrostatic characteristics of the completed laminated electrophotographic photoreceptor 1 were evaluated, the results shown in Tables 1 and 2 were obtained.

(Comparative Example 3) An oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 was formed by using the same oxotitanium phthalocyanine as in Comparative Example 1, and the oxotitanium phthalocyanine-deposited film was exposed without being exposed. According to the same procedure as in Example 6, the laminated electrophotographic photoreceptor 1 was completed. When the electrostatic characteristics of the completed laminated electrophotographic photoreceptor 1 were evaluated, the results shown in Tables 1 and 2 were obtained.

(Comparative Example 4) An oxotitanium phthalocyanine vapor-deposited film formed according to the same procedure as in Comparative Example 1 was exposed to acetone vapor for 30 minutes, and the other procedures were the same as in Example 6. Thus, a laminated electrophotographic photoreceptor 1 was completed. When the electrostatic characteristics of the completed laminated electrophotographic photoreceptor 1 were evaluated, the results shown in Tables 1 and 2 were obtained.

Comparative Example 5 An oxotitanium phthalocyanine vapor-deposited film as the charge generation layer 3 was formed by using oxotitanium phthalocyanine synthesized without acid paste treatment, and then, 2-methyl-4-dibenzylaminobenzaldehyde was used. -N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl)
The charge transport layer 4 is formed after using a transport layer forming coating solution obtained by dissolving -4,4-diphenyl-1,3-butadiene with chloroform. Then, the same procedure as in Example 6 was employed to complete the laminated electrophotographic photoreceptor 1, and the same evaluation as in Example 18 was performed. The results shown in Table 2 were obtained. ing.

(Comparative Example 6) An oxotitanium phthalocyanine vapor-deposited film was formed by using oxotitanium phthalocyanine purified without being subjected to acid paste treatment, and the same procedure as in Example 6 was employed. Photoreceptor 1 was completed. Then, Example 1
When the same evaluation as in Example 8 was performed, the results shown in Table 2 were obtained.

Further, when each of Examples 1 to 18 described above and each of Comparative Examples 1 to 6 were compared with each other, it was found that Examples 1 to 18 were explained. The laminated electrophotographic photoreceptor 1 according to the present embodiment has higher sensitivity to long-wavelength light such as a semiconductor laser beam, and has excellent sensitivity and chargeability repetition characteristics. It has been clarified that stability when left in the dark for a long time is also improved.

[0073]

As described above, according to the first aspect of the present invention,
In the laminated electrophotographic photoreceptor according to the present invention, since the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is exposed to a mixed vapor containing at least an aromatic organic solvent and water, the charge generation layer Has high sensitivity to semiconductor laser light and has little occurrence of carrier trapping and recombination. Therefore, it is excellent in sensitivity and chargeability, and has excellent repetition stability such as sensitivity and chargeability, and also has a photosensitive layer for electrophotography having a photosensitive layer excellent in long-term stability in the dark. Since the body is formed, an effect that a high-quality image can be formed for a long period of time can be obtained.
In the laminated electrophotographic photoreceptor according to the second aspect, since the aromatic organic solvent is chlorobenzene, toluene, or a mixture thereof, disorder of crystal orientation in the oxotitanium phthalocyanine vapor-deposited film is further increased. As a result, the sensitivity and the chargeability, and the effect of further improving the stability of these repetitions are obtained.

In the laminated electrophotographic photoreceptor according to the third aspect of the present invention, the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is exposed to at least a mixed vapor of chlorinated aliphatic hydrocarbon and water. Therefore, a photosensitive layer having excellent sensitivity and chargeability, excellent repeatability such as sensitivity and chargeability, and excellent long-term stability in the dark can be obtained. Therefore, as in the case of the first aspect, it is possible to form a high-quality image for a long period of time. Further, in the laminated electrophotographic photoreceptor according to claim 4, since the aromatic organic solvent is supposed to be chloroform, dichloroethane, or a mixture thereof, the crystal orientation of the oxotitanium phthalocyanine vapor-deposited film is reduced. As a result of further reducing the disturbance, an effect is obtained in which the sensitivity, the charging property, and the repetition stability thereof are remarkably improved.

The oxotitanium phthalocyanine vapor-deposited film, which is the charge generation layer of the laminated electrophotographic photosensitive member according to claim 5 of the present invention, has a maximum peak wavelength of a light absorption spectrum of 780 ± 10 nm. It has excellent sensitivity to laser light and less carrier trapping and recombination. As a result, a laminated electrophotographic photoreceptor having excellent sensitivity and chargeability and excellent repetition stability thereof can be formed. On the other hand, the laminated electrophotographic photoreceptor according to claim 6 is characterized in that the thickness of the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is in the range of 0.03 μm to 0.5 μm. When such a configuration is adopted, a sufficient amount of carriers can be obtained, and the dark decay is reduced, so that the charging potential can be kept high. As a result, good sensitivity is obtained, and the sensitivity and the charging property are repeated. The effect is obtained that the stability is further improved.

The oxotitanium phthalocyanine vapor-deposited film, which is the charge generation layer of the multilayer electrophotographic photosensitive member according to claim 7 of the present invention, is formed using oxotitanium phthalocyanine obtained by acid paste treatment. Yes, the acid paste treatment removes impurities in the pigment particles, so that excellent sensitivity and chargeability can be obtained, and the effect of producing a photosensitive layer with excellent long-term stability in the dark can be obtained. Can be The oxotitanium phthalocyanine vapor-deposited film in the multilayer electrophotographic photoreceptor according to claim 8 is formed using oxotitanium phthalocyanine purified by sublimation after acid paste treatment. In this case, Since the content of impurities in the pigment is extremely small, and the amount of impurities taken into the vapor deposition film during the vapor deposition process is extremely small, the electrical characteristics of the oxotitanium phthalocyanine vapor deposition film are greatly improved, and the charge retention characteristics and sensitivity are further improved. As a result, the image quality can be improved to such an extent that image noise called a black point is hardly recognized in actual image formation.

The charge transport layer of the layered electrophotographic photoreceptor according to the ninth aspect of the present invention is formed by using a transport layer forming coating liquid, and the transport layer forming coating liquid is charged. Since the transport agent and the resin binder are dissolved in toluene or chloroform, they do not change the crystal form of the oxotitanium phthalocyanine vapor-deposited film after the exposure treatment, and furthermore, a charge transport layer having high transparency. As a result, the sensitivity of the photosensitive layer can be further improved. And
In the photoreceptor for laminated electrophotography according to claim 10, the charge transporting agent is 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis.
(p-diethylaminophenyl) -4,4-diphenyl-
Since it is a mixture with 1,3-butadiene, a photosensitive layer having excellent ozone resistance can be obtained. Further, since the charge transporting agent is 4-N, N-diphenylamino-α-phenylstilbene, the laminated electrophotographic photoreceptor according to claim 11 is excellent in sensitivity and chargeability.
It is possible to obtain a photosensitive layer having not only excellent repetition stability but also excellent ozone resistance.

The method for producing a laminated electrophotographic photoreceptor according to the twelfth aspect of the present invention comprises the steps of laminating at least a charge generation layer and a charge transport layer on a conductive support in this order. It is a method of manufacturing a photoreceptor, the step of forming a charge generation layer, the step of depositing oxotitanium phthalocyanine on a conductive support, the obtained oxotitanium phthalocyanine deposited film of an aromatic organic solvent and water Since it includes a step of performing an exposure treatment with a mixed vapor, by adopting such a method, the sensitivity and the chargeability are excellent, and the sensitivity and the chargeability are also excellent in the repetition stability, In addition, an effect is obtained that a photosensitive layer having excellent long-term stability in the dark can be rationally and stably manufactured. And Claim 13
The method for producing a laminated electrophotographic photoreceptor according to the present invention comprises the steps of: depositing oxotitanium phthalocyanine on a conductive support; and mixing the resulting oxotitanium phthalocyanine deposited film with a mixed vapor of chlorinated aliphatic hydrocarbon and water. And exposing the charge-generating layer, which has excellent sensitivity and chargeability, and has excellent repetition stability and long-term stability in the dark. This makes it possible to obtain a photosensitive layer excellent in the above ratio reasonably and stably.

The method for manufacturing a laminated electrophotographic photoreceptor according to claim 14 of the present invention is characterized in that the exposure time of the oxotitanium phthalocyanine vapor-deposited film is in the range of 30 seconds to 3 hours. When the manufacturing method is adopted, the maximum peak wavelength of the light absorption spectrum of the entire oxotitanium phthalocyanine vapor-deposited film formed over the entire area of the conductive support even if the conductive support has a long drum shape. The effect of being able to modify to a crystal form showing 780 ± 10 nm is obtained. Claim 15
The method of manufacturing a laminated electrophotographic photoreceptor according to the present invention is characterized in that the step before forming the charge generation layer includes a step of subjecting oxotitanium phthalocyanine to an acid paste treatment, and this manufacturing method may adversely affect electrical characteristics. In addition to the effect of easily removing the impurities giving the following effect, a photosensitive layer having excellent sensitivity and chargeability and having excellent long-term stability in the dark can be produced.

In the method of manufacturing a laminated electrophotographic photoreceptor according to claim 16 of the present invention, the step before the formation of the charge generation layer includes the step of subjecting oxotitanium phthalocyanine to acid paste treatment and then sublimating and refining. When this production method is adopted, the electric characteristics of the oxotitanium phthalocyanine vapor-deposited film are greatly improved, so that the charge retention characteristics and sensitivity of the photosensitive layer are further improved, and the black spot and The image quality at the time of actual image formation can be improved to such an extent that image noise is hardly recognized. Further, in the method of manufacturing a laminated electrophotographic photoreceptor according to claim 17, in the step of forming the charge transport layer, the transport layer forming coating liquid obtained by dissolving the charge transport agent and the resin binder in toluene or chloroform is charged. It is characterized by including a step of dip coating on the oxotitanium phthalocyanine vapor-deposited film that is the generation layer, and when such a production method is adopted, a highly transparent charge transport layer is provided, and The effect is obtained that a photosensitive layer with further improved sensitivity, that is, a photosensitive layer having a high initial charging potential and less charge unevenness can be efficiently manufactured.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating a configuration of a laminated electrophotographic photosensitive member according to an embodiment.

FIG. 2 is an explanatory diagram showing a change state of a light absorption spectrum of a vapor-deposited oxotitanium phthalocyanine film by an exposure treatment when a mixed vapor containing chlorobenzene and water is used.

FIG. 3 is an explanatory diagram showing a change state of a light absorption spectrum of a vapor-deposited oxotitanium phthalocyanine film after an exposure treatment when a mixed vapor containing toluene and water is used.

FIG. 4 is an explanatory diagram showing a change state of a light absorption spectrum of a vapor-deposited oxotitanium phthalocyanine film after an exposure treatment when a mixed vapor containing chloroform and water is used.

FIG. 5 is an explanatory diagram showing a change state of a light absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after an exposure treatment when using a mixed vapor containing dichloroethane and water.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 laminated electrophotographic photoreceptor 2 conductive support 3 charge generation layer 4 charge transport layer 5 organic photosensitive layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuya Sato 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (72) Inventor Masayuki Ono 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (17)

[Claims] 1. A laminated electrophotographic photoconductor in which at least a charge generation layer and a charge transport layer are laminated in this order on a conductive support, wherein the charge generation layer is an oxotitanium phthalocyanine vapor-deposited film, The oxotitanium phthalocyanine vapor-deposited film is subjected to exposure treatment with a mixed vapor containing at least an aromatic organic solvent and water. 2. The laminated electrophotographic photoconductor according to claim 1, wherein the aromatic organic solvent is chlorobenzene or toluene,
Alternatively, a laminated electrophotographic photoconductor, which is a mixture thereof. 3. A laminated electrophotographic photoconductor in which at least a charge generation layer and a charge transport layer are laminated on a conductive support in this order, wherein the charge generation layer is an oxotitanium phthalocyanine vapor-deposited film, A laminated electrophotographic photoreceptor, wherein the oxotitanium phthalocyanine vapor-deposited film has been exposed to a mixed vapor containing at least chlorinated aliphatic hydrocarbon and water. 4. The laminated electrophotographic photoconductor according to claim 3, wherein the chlorinated aliphatic hydrocarbon is chloroform, dichloroethane, or a mixture thereof. Photoreceptor. 5. The laminated electrophotographic photoreceptor according to claim 1, wherein the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer has a maximum peak wavelength of a light absorption spectrum of 780. ± 1
A layered electrophotographic photoreceptor having a thickness of 0 nm. 6. The laminated electrophotographic photoconductor according to claim 1, wherein the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer has a thickness of 0.03 μm to 0.1 μm. A layered electrophotographic photoreceptor having a thickness of up to 5 μm. 7. The laminated electrophotographic photoreceptor according to claim 1, wherein the oxotitanium phthalocyanine vapor-deposited film serving as a charge generation layer is obtained by an acid paste treatment. A laminated electrophotographic photoreceptor characterized by being formed using titanium phthalocyanine. 8. The laminated electrophotographic photoreceptor according to claim 1, wherein the oxotitanium phthalocyanine vapor-deposited film as the charge generation layer is subjected to acid paste treatment and then sublimation purification. A laminated electrophotographic photoconductor, which is formed using the oxotitanium phthalocyanine obtained by the above method. 9. The layered electrophotographic photoreceptor according to claim 1, wherein the charge transport layer is formed using a coating liquid for forming a transport layer. A layered electrophotographic photoreceptor, wherein the coating liquid for use is obtained by dissolving a charge transport agent and a resin binder in toluene or chloroform. 10. The layered electrophotographic photoconductor according to claim 9, wherein the charge transporting agent is 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone;
A laminated electrophotographic photoconductor, which is a mixture with 1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene. 11. The multilayered electrophotographic photoconductor according to claim 9, wherein the charge transporting agent is 4-N, N-diphenylamino-α-phenylstilbene. Photoreceptor. 12. A method for producing a laminated electrophotographic photoconductor in which at least a charge generation layer and a charge transport layer are laminated in this order on a conductive support, wherein the step of forming the charge generation layer comprises: The method includes a step of depositing oxotitanium phthalocyanine on the conductive support, and a step of exposing the obtained oxotitanium phthalocyanine deposited film to a mixed vapor containing at least an aromatic organic solvent and water. A method for producing a laminated electrophotographic photoreceptor, comprising: 13. A method for producing a laminated electrophotographic photoconductor in which at least a charge generation layer and a charge transport layer are laminated in this order on a conductive support, wherein the step of forming the charge generation layer comprises: A step of depositing oxotitanium phthalocyanine on the conductive support, and a step of exposing the obtained oxotitanium phthalocyanine deposited film to a mixed vapor containing at least a chlorinated aliphatic hydrocarbon and water. A method for producing a laminated electrophotographic photoreceptor. 14. The method for producing a laminated electrophotographic photoconductor according to claim 12, wherein the exposure time of the oxotitanium phthalocyanine vapor-deposited film is:
A method for producing a laminated electrophotographic photoreceptor, wherein the time is within a range of 30 seconds to 3 hours. 15. The method according to claim 12, wherein the step of forming the charge generation layer is a step of performing an acid paste treatment on oxotitanium phthalocyanine. A method for producing a laminated electrophotographic photoreceptor, comprising: 16. The method according to claim 12, wherein in the step of forming the charge generation layer, oxotitanium phthalocyanine is treated with an acid paste. A method for producing a laminated electrophotographic photoreceptor, comprising a step of sublimating and refining the photoconductor. 17. The method according to claim 12, wherein the step of forming the charge transport layer comprises using a charge transport agent and a resin binder as toluene or chloroform. A process for dip-coating a transport layer forming coating solution dissolved in (1) above on an oxotitanium phthalocyanine vapor-deposited film as a charge generating layer, the method comprising the steps of: