JPH10312074A - Lam inated electrophotographic photoreceptor and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated electrophotographic photoreceptor which has layers of a pigment vapor deposition film and a charge transfer layer and which shows high sensitivity for semiconductor laser light and excellent stability for repeated use in the photoreceptor characteristics such as sensitivity and electrification property. SOLUTION: Oxotitanium phthalocyanine is vapor deposited to 0.1 μm thickness on a conductive substrate 2 in 10<-5> to 10<-6> Torr vacuum. This vapor deposition film is dipped in a water-added solvent comprising ethylene glycolalkyletheracetate-water, propyleneglycol alkyletheracetate-water, ethyleneglycoldiacetate-water or θ-butylolactone-water. Then the charge transfer layer 5 is formed on the charge producing layer 4 comprising the oxotitanium phthalocyanine vapor deposition film after the dipping treatment to obtain the laminated electrophotographic photoreceptor.

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 such as a copying machine, a printer and a facsimile, and a laminated electrophotographic photosensitive member using an oxotitanium phthalocyanine vapor-deposited film which can be used for the same. The present invention relates to a photoreceptor and a method for producing the same, and more particularly, to a laminated electrophotographic photoreceptor capable of maintaining high sensitivity and excellent electrophotographic characteristics and high image quality, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, electrophotographic apparatuses have attracted attention for their advantages such as high speed, low noise, high image quality, and the ability to record on plain paper. Are rapidly spreading. Also, as a recent trend, especially in the field of printers and facsimile machines, the form of use has been shifting from office use to personal use.
While cost reduction, maintenance-free, and the like are required, with the improvement of image processing technology, there is a demand for an image forming technology for higher resolution and improved image quality.

As a photoreceptor used for the electrophotographic apparatus, an organic photoreceptor containing an organic photoconductive substance has recently been developed because of its advantages such as easy film formation, low cost and no pollution. Has been In particular, the development of an organic photoreceptor having high sensitivity in a long wavelength region suitable for a laser beam printer or a facsimile using a semiconductor laser as an exposure light source is remarkable.

[0004] Most of the organic photoreceptors put to practical use have a laminated organic photoreceptor 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. It is. More specifically, the photosensitive layer is formed by forming a thin charge generation layer and forming a relatively thick charge transport layer thereon, in which case the charge generation layer has a function of generating carriers. The charge transport layer has a function of transporting carriers, a function of maintaining a charged potential of the photoconductor, and a function of maintaining mechanical strength of the photoconductor.

In recent years, phthalocyanine, which has high sensitivity in the long wavelength region, which is the oscillation wavelength region of a semiconductor laser, has attracted attention as a charge generation material used in the charge generation layer. Type electrophotographic photosensitive members have been put to practical use.

A method for forming a charge generating layer using oxotitanium phthalocyanine as a charge generating agent includes:
There are roughly two methods. One uses a coating material in which a certain crystalline oxotitanium phthalocyanine is dispersed in a solvent together with a binder resin.
This is a method of forming the charge generation layer as a thin layer having a thickness of about 0.5 μm.

Another method is to deposit oxotitanium phthalocyanine on a conductive support, and then subject the oxotitanium phthalocyanine deposited film to solvent vapor treatment to form a charge generation layer. For example, JP-A-59-16
According to 6959, the film immediately after vapor deposition obtained by vapor-depositing oxotitanium phthalocyanine has an absorption peak at 720 nm. For example, the absorption peak can be shifted to 830 nm by vapor treatment of tetrahydrofuran,
The X-ray diffraction spectrum of the charge generation layer after the treatment is advantageous for the semiconductor laser light, and the Bragg angle (2
θ) 7.5 °, 12.6 °, 13.0 °, 25.4
It is reported that it has strong diffraction peaks at °, 26.2 ° and 28.6 °.

[0008]

As described above, a method for forming a charge generation layer using oxotitanium phthalocyanine generally includes a method of coating and forming a thin film using a coating material in which oxotitanium phthalocyanine is dispersed. There is a method of forming a deposited film of oxotitanium phthalocyanine, but a thin film having a uniform concentration can be easily formed, and
The latter method of forming a vapor-deposited film of oxotitanium phthalocyanine is considered to be more advantageous because it is excellent in stability of film quality. However, Japanese Patent Application Laid-Open No.
No. 166959, the oxotitanium phthalocyanine vapor-deposited film is exposed to a vapor of a soluble solvent to shift the absorption wavelength of the light to the longer wavelength side, and the oxotitanium phthalocyanine vapor-deposited film after the vapor treatment is used as a charge generation layer. In the case of the laminated photoreceptor used in the above method, the vaporization of the oxotitanium phthalocyanine vapor-deposited film reduces the photoreceptor's sensitivity and charging properties such as charging potential, and in particular, the sensitivity and repetition stability of the charging properties. For this reason, various studies have been made on a process for shifting the absorption wavelength of light of the oxotitanium phthalocyanine vapor-deposited film to the longer wavelength side, but still in a laminated photoreceptor using the oxotitanium phthalocyanine vapor-deposited film as a charge generation layer. In fact, it has not been possible to obtain a photoreceptor having high sensitivity to semiconductor laser light and having sufficiently small deterioration of photoreceptor characteristics such as sensitivity and chargeability in a repeated image forming process.

The present invention has been made in view of the above-mentioned problems, and has a high sensitivity to a semiconductor laser beam and a laminated type excellent in repetition stability of photoreceptor characteristics such as sensitivity and chargeability. An object of the present invention is to provide a method for producing a photoreceptor for electrophotography and a deposited oxotitanium phthalocyanine film that can be used for the photoreceptor.

[0010]

In order to achieve this object, a laminated electrophotographic photoreceptor of the present invention comprises a laminate comprising at least a charge generation layer and a charge transport layer laminated on a conductive support. In the electrophotographic photoreceptor, the charge generation layer is an oxotitanium phthalocyanine vapor-deposited film, at least one selected from alkylene glycol alkyl ether acetate-water, alkylene glycol diacetate-water, and γ-butyrolactone-water. It is characterized by being immersed and treated in a hydrogenation solvent containing a compound.
Thereby, the oxo-titanium phthalocyanine vapor-deposited film has excellent sensitivity to semiconductor laser light due to its unique crystal structure, and becomes a charge generation layer with less carrier trapping and recombination. A photoreceptor is obtained which has good chargeability and excellent repetition stability.

Next, the method for producing a laminated electrophotographic photoreceptor of the present invention comprises a method for producing a laminated electrophotographic photoreceptor comprising a charge generating layer and a charge transporting layer laminated on a conductive support. Wherein oxotitanium phthalocyanine is vapor-deposited on a support, and the obtained oxotitanium phthalocyanine vapor-deposited film is subjected to alkylene glycol alkyl ether acetate-water, alkylene glycol diacetate-
The charge generation layer is characterized by being immersed in a hydrogenation solvent containing at least one compound selected from water and γ-butyrolactone-water.

According to the method of the present invention, the laminated electrophotographic photosensitive member of the present invention can be efficiently, rationally and stably manufactured. In the lamination type electrophotographic photoreceptor and the method for producing the same, the alkylene group of the alkylene glycol alkyl ether acetate is preferably at least one organic group selected from an ethylene group, a propylene group and a butylene group. In particular, in ethylene glycol alkyl ether acetate, the alkyl group is a methyl group,
It is preferable to use one selected from ethyl groups or a mixture thereof. With such a structure, the above-described sensitivity and chargeability, and the effect of improving their repetition stability are more remarkably exhibited. .

[0013] In the laminated electrophotographic photoreceptor and the method of manufacturing the same, the alkyl group of the alkylene glycol alkyl ether acetate is preferably at least one organic group selected from a methyl group and an ethyl group. With such a configuration, the above-described effects of improving the sensitivity and the charging property and the repetition stability thereof are more remarkably exhibited.

In the laminated electrophotographic photoreceptor and the method for producing the same, the alkylene group of the alkylene glycol diacetate is preferably at least one organic group selected from an ethylene group, a propylene group and a butylene group. . The oxotitanium phthalocyanine vapor-deposited film immersed in a hydrogenation solvent consisting of propylene glycol alkyl ether acetate and water, which is the charge generation layer, has excellent sensitivity to semiconductor laser light due to its unique crystal structure. Thus, since the charge generation layer has less carrier trapping and recombination, excellent sensitivity and chargeability can be obtained, and a photoreceptor having excellent repetition stability thereof can be obtained. Also, the oxotitanium phthalocyanine vapor-deposited film immersed in a hydrogenation solvent consisting of ethylene glycol diacetate and water, which is a charge generation layer, has excellent sensitivity to semiconductor laser light due to its unique crystal structure. In addition, since the charge generation layer has less carrier trapping and recombination, excellent sensitivity and chargeability can be obtained, and a photoreceptor having excellent repetition stability thereof can be obtained.

In the above-mentioned laminated electrophotographic photoreceptor and the method of manufacturing the same, the charge transport layer is provided on the charge generation layer.
It is preferably formed by applying a coating solution obtained by dissolving at least a charge transport agent and a resin binder in toluene or chloroform. With such a configuration, a highly transparent charge transport layer can be formed without changing the crystal form of the oxotitanium phthalocyanine vapor-deposited film after the immersion treatment, and the sensitivity is further improved.

In the above-mentioned laminated electrophotographic photoreceptor and the method for producing the same, the charge transporting agent is 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis (p- It is preferably a mixture with (diethylaminophenyl) -4,4-diphenyl-1,3-butadiene. Thereby, the ozone resistance becomes excellent.

In the above-mentioned laminated electrophotographic photoreceptor and the method for producing the same, the charge transporting agent is preferably 4-N, N-diphenylamino-α-phenylstilbene. Thereby, the ozone resistance becomes excellent.

[0018]

FIG. 1 is a cross-sectional view schematically showing the structure of a laminated electrophotographic photosensitive member according to one embodiment of the present invention. In FIG. 1, reference numeral 1 denotes a laminated electrophotographic photosensitive member. The organic photosensitive layer 3 includes a charge generation layer 4 and a charge transport layer 5 laminated on a conductive support 2 in this order.

The conductive support 2 is a substrate made of a conductive material known per se, for example, a metal material such as aluminum, or a conductive plastic (for example, an insulating resin such as a phenol resin or a conductive particle such as carbon). ), Aluminum iodide, copper iodide, chromium oxide,
Alternatively, a substrate made of glass or the like coated with a conductive metal compound such as tin oxide is used. The form of the substrate is various forms such as a drum form (pipe form), a plate form, and a belt form, and is not particularly limited.

The charge generation layer 4 is formed by depositing oxotitanium phthalocyanine on the conductive support 2 in a vacuum, and depositing the oxotitanium phthalocyanine deposited film on ethylene glycol alkyl ether acetate-water, propylene glycol alkyl ether acetate-water, Glycol diacetate-water or γ-butyrolactone-
It is formed by immersion in a hydrogenation solvent comprising water. By this treatment, oxotitanium phthalocyanine becomes a charge generation layer with less carrier trapping and recombination.

The higher the purity of the oxotitanium phthalocyanine, the better. Examples thereof include a method of heating oxotitanium phthalocyanine under reflux in quinoline and a method of sublimating and purifying oxotitanium phthalocyanine.

As the ethylene glycol alkyl ether acetate or the propylene glycol alkyl ether acetate constituting the hydrogenated solvent, those having an alkyl group having 1 to 4 carbon atoms or a mixture of two or more selected from these are generally used. be able to. In particular, from the viewpoint of drying the deposited film after the treatment, it is preferable to use, as the alkyl group, a methyl group or an ethyl group whose boiling point is not so high. The mixing ratio of the organic solvent and water is 100: 1 to 100: 50, preferably 100: 2 to 100: 40 in terms of volume ratio (organic solvent: water). By setting the volume ratio of the organic solvent to water within the range of 100: 2 to 100: 40, the photoconductor using the obtained oxotitanium phthalocyanine vapor-deposited film as a charge generation layer has excellent sensitivity and chargeability. It will be. If the volume ratio of the organic solvent to water is out of this range and the volume ratio of the organic solvent is too large or too small, the obtained photoreceptor has particularly low sensitivity.

The thickness of the deposited oxotitanium phthalocyanine film is about 0.03 to 0.5 μm, preferably about 0.1 to 0.2 μm, due to its characteristics. This indicates that if the film thickness is too small, it is difficult to obtain sufficient sensitivity because the amount of generated charges (carriers) is small. If the film thickness is too large, dark decay increases to lower the charging potential, and This is because there is a tendency that the repetition stability of the sensitivity tends to decrease. That is, when the film thickness is set to about 0.03 to 0.5 μm, a sufficient amount of carriers can be obtained, and dark decay can be sufficiently reduced.

The immersion time in the hydrogenated solvent comprising the organic solvent and water is in the range of 30 seconds to 3 hours, preferably 10 minutes to 60 minutes. The charge transporting layer 5 is prepared by dissolving a charge transporting agent and a binder resin in a suitable solvent for dissolving the same to form a coating for the charge transporting layer, and applying the coating on the charge generating layer 4 by a conventionally known coating method. It is formed by forming a film and drying the coating film.

Examples of the charge transporting agent include heterocyclic compounds such as oxazole, oxadiazole and pyrazoline;
Examples include hydrazone compounds, butadiene compounds, stilbene compounds, and various derivatives of these compounds. Specific examples include, for example, 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone, 4-diethylaminobenzaldehyde-N, N-diphenylhydrazone, 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 one or more of these are used. Especially,
2-methyl-4-dibenzylaminobenzaldehyde-
N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3
If both butadiene are used or 4-N,
When N-diphenylamino-α-phenylstilbene is used, it is possible to form a photosensitive layer having particularly high sensitivity and less deterioration by ozone. In addition, 2-methyl-4-dibenzylaminobenzaldehyde-N, N
When both -diphenylhydrazone and 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene are used, the mixing ratio of both is weight ratio (2-methyl-4-dibenzyl). Aminobenzaldehyde-N, N-diphenylhydrazone: 1,1-bis (p-
Diethylaminophenyl) -4,4-diphenyl-1,
3-butadiene), and is generally preferably in the range of 99: 1 to 30:70. This is because sensitivity tends to decrease when there is too much 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone, and 1,1
When the content of -bis (p-diethylaminophenyl) -4,4-diphenyl-1,3-butadiene is too large, the ozone resistance tends to decrease. This is because good ozone resistance can be obtained.

Examples of the binder resin include various resins such as polyester, polycarbonate, polysulfone, and polymethyl methacrylate. As the solvent, various organic solvents such as ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran, chlorinated hydrocarbons such as methylene chloride and chloroform, and aromatic hydrocarbons such as benzene and toluene are used. A particularly preferred solvent is chloroform or toluene, and when these are used, it is possible to form a highly transparent charge transport layer without changing the crystal form of the oxotitanium phthalocyanine vapor-deposited film after the immersion treatment with the hydrogenated solvent. As a result, the sensitivity of the photoconductor is improved.

Although the composition of the paint is not particularly limited, generally, the charge transporting agent and the binder resin are used such that their weight ratio (charge transporting agent: binder resin) is in the range of 60:40 to 40:60. The charge transporting agent and the binder resin are dissolved in a solvent such that the total solid content concentration is 10 to 40% by weight.

The coating method of the paint is not particularly limited, but it is preferable to use a so-called dip coating method of forming a coating film by immersing an object to be coated in the paint and lifting it up.
By using such a dip coating method, a coating film having a relatively large thickness and a uniform thickness can be easily formed in a short time.

The thickness of the charge transport layer 5 is generally several μm to several tens μm, preferably 15 to 30 μm. By setting the film thickness in such a range, the initial charging potential of the photoconductor can be set sufficiently high.

As described above, according to one embodiment of the present invention, oxotitanium phthalocyanine is contained in an amount of 10 ⁻⁵ to 10 ⁻⁵ .
Vacuum is deposited on the conductive substrate (2) at a thickness of 0.1 μm under a vacuum of 10 ⁻⁶ torr. This deposited film is immersed in a hydrogenated solvent composed of ethylene glycol alkyl ether acetate-water, propylene glycol alkyl ether acetate-water, ethylene glycol diacetate-water, or γ-butyrolactone-water. The charge generation layer comprising the immersed oxotitanium phthalocyanine film
By forming the charge transport layer (5) on (4), a laminated electrophotographic photoconductor can be obtained.

[0031]

【Example】

(Example 1) (1) Synthesis of oxotitanium phthalocyanine pigment 1-chloronaphthalene (770 ml) in a three-necked flask
1,3-diiminoisoindoline (113 g) is suspended in the mixture, and tetra-n-butyl titanate (75 g) is stirred under stirring.
And heated at 195-205 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, the mixture was allowed to cool to 130 ° C., and was then filtered. The separated product was 1-chloronaphthalene (100 m) heated to 100 ° C.
After washing in 1), washing was sufficiently performed with ethanol (1000 ml). This is dimethylformamide (500m
1) 3 times of hot suspension washing at 80 ° C. for 1 hour using
Next, the suspension was washed twice with ethanol (500 ml) at 60 ° C. for 1 hour, and then dried at 50 ° C. in vacuo. Then, the obtained pigment was refluxed and heated in quinoline (2000 ml) with stirring for 4 hours, allowed to stand overnight, cooled in an ice-water bath for 1 hour, and filtered. After sufficiently washing with ethanol, vacuum drying was performed at 50 ° C. for 10 hours and at 100 ° C. for 10 hours. The yield was 75 g. (2) Production of Laminated Photoreceptor Titanyl phthalocyanine obtained as described above was
Under a vacuum of 0 ^-5 to 10 ^-6 torr, the film was deposited to a thickness of 0.1 μm on an aluminum plate. This deposited film was treated with ethylene glycol methyl ether acetate-water (4% by volume).
0: 2) and left for 60 minutes in a hydrogenated solvent.
By this immersion treatment, the maximum absorption wavelength range shifted to the longer wavelength side. FIG. 2 shows the change in absorption spectrum due to the treatment with a hydrogenated solvent composed of ethylene glycol methyl ether acetate-water. FIG. 2A shows an absorption spectrum of oxotitanium phthalocyanine (TiOPc) immediately after vapor deposition, and has an absorption peak around 720 nm. FIG.
(B) shows an absorption spectrum as a result of performing a hydrogenated solvent treatment comprising ethylene glycol methyl ether acetate-water, and it can be seen that the absorption peak is around 780 nm and shifts to a longer wavelength side.

Next, 20 parts by weight of 4-N, N-diphenylamino-α-phenylstilbene and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.) were placed on the charge generation layer comprising the oxotitanium phthalocyanine vapor-deposited film thus obtained. Industrial Co., Ltd., trade name Iupilon Z-300) 20
A charge transport layer was provided by dip coating with a coating liquid consisting of 100 parts by weight of toluene and 100 parts by weight of toluene so that the film thickness after drying was 20 μm, thereby completing a photoreceptor.

Next, the electrostatic characteristics of the photoreceptor were measured using an electrostatic copying paper tester (Model EPA-8 manufactured by Kawaguchi Electric Works, Ltd.).
100). The evaluation showed that the corona current was -3.
The initial charging potential when the photoconductor is negatively charged in a dark place by corona discharge at an applied voltage set to be 0 μA is Vma
x (V), the surface potential after one second of dark decay is V0 (V), and the charge retention rate after one second of dark decay is D. 2.1 μJ / cm ² · s with a peak at 800 nm
Irradiated with monochromatic light of energy of 4 seconds, the exposure amount at which the surface potential becomes 1 / 2V0 and 1 / 5V0 is E1 /
2, E1 / 5 (μJ / cm ² ), and the surface potential 4 seconds after exposure was measured as residual potential VR (V). The results are shown in (Table 1).

Using the sample prepared as described above, a repetition test was performed 1000 times under the same measurement conditions, and the repetition stability of the electrostatic characteristics (sensitivity and charging characteristics) was also evaluated. The results are shown in (Table 2). The residual potential VR in the repetition characteristics was measured by measuring the residual potential two seconds after exposure.

(Example 2) Instead of the immersion treatment with a hydrogenated solvent consisting of ethylene glycol methyl ether acetate-water of Example 1, ethylene glycol ethyl ether acetate-water (40:40 by volume ratio) was used as a treatment solvent.
A photoconductor was prepared in the same manner as in Example 1 except that 1) was used, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in (Tables 1 and 2).

FIG. 3 shows the absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the hydrogenation solvent treatment comprising the above ethylene glycol ethyl ether acetate-water. From FIG. 3, it can be seen that it has the maximum absorption peak wavelength at 778 nm.

(Example 3) Instead of the immersion treatment with the hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water of Example 1, propylene glycol methyl ether acetate-water (40:40 by volume ratio) was used as a treatment solvent.
A photoconductor was prepared in the same manner as in Example 1 except that 1) was used, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in (Tables 1 and 2).

FIG. 4 shows an absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the hydrogenation solvent treatment comprising propylene glycol methyl ether acetate-water. From this figure, it can be seen that it has a maximum absorption peak wavelength at 780 nm.

(Example 4) Instead of the immersion treatment with the hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water of Example 1, propylene glycol ethyl ether acetate-water (40:40 by volume ratio) was used as the treatment solvent.
A photoconductor was prepared in the same manner as in Example 1 except that 1) was used, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in (Tables 1 and 2).

FIG. 5 shows an absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the hydrogenation solvent treatment comprising propylene glycol ethyl ether acetate-water. From this figure, it can be seen that it has a maximum absorption peak wavelength at 782 nm.

Example 5 Instead of the immersion treatment in Example 1 with a hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water, ethylene glycol diacetate-water (40: 1 in volume ratio) was used as a treatment solvent. A photoconductor was prepared in the same manner as in Example 1 except that
Evaluation of electrostatic characteristics was performed in the same manner as described above. The results are shown in Table 1
To 2).

FIG. 6 shows an absorption spectrum of the oxotitanium phthalocyanine vapor-deposited film after the treatment with the hydrogenation solvent consisting of ethylene glycol diacetate-water. From this figure, it can be seen that it has a maximum absorption peak wavelength at 780 nm.

Example 6 Instead of the immersion treatment in Example 1 with a hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water, γ-butyrolactone-water (40:10 by volume) was used as a treatment solvent. Except for the above, a photoconductor was prepared in the same manner as in Example 1, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in (Tables 1 and 2).

FIG. 7 shows the above-mentioned γ-butyrolactone-
4 shows an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after treatment with a hydrogenated solvent composed of water. From this figure, it can be seen that it has a maximum absorption peak wavelength at 828 nm.

Example 7 Instead of 20 parts by weight of 4-N, N-diphenylamino-α-phenylstilbene of Example 1, 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone 18 was used. Parts by weight and 1,1-bis (p-diethylaminophenyl) -4,4
-Except that 2 parts by weight of diphenyl-1,3-butadiene was used as a charge transporting agent and chloroform was used as a solvent instead of using toluene to form a charge transporting layer.
A photoconductor was prepared in the same manner as in Example 1, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in Tables 1-2.
Shown in

(Example 8) Instead of the immersion treatment with a hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water of Example 7, ethylene glycol ethyl ether acetate-water (40:40 by volume ratio) was used as a treatment solvent.
A photoconductor was prepared in the same manner as in Example 7, except that 1) was used, and the electrostatic characteristics were evaluated in the same manner as in Example 7. The results are shown in (Tables 1 and 2).

Example 9 Instead of the immersion treatment in Example 7 with a hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water, ethylene glycol diacetate-water (40: 1 in volume ratio) was used as a treatment solvent. A photoconductor was prepared in the same manner as in Example 7 except that
Evaluation of electrostatic characteristics was performed in the same manner as described above. The results are shown in Table 1
To 2).

Example 10 Instead of the immersion treatment in Example 7 with a hydrogenation solvent consisting of ethylene glycol methyl ether acetate-water, γ-butyrolactone-water (40:10 by volume) was used as a treatment solvent. Except for the above, a photoconductor was prepared in the same manner as in Example 7, and the electrostatic characteristics were evaluated in the same manner as in Example 7. The results are shown in (Tables 1 and 2).

Comparative Example 1 A photoreceptor was prepared by providing a charge transport layer in the same manner as in Example 1 except that the oxotitanium phthalocyanine vapor-deposited film was exposed to acetone vapor for 30 minutes. To evaluate the electrostatic characteristics. The results are shown in (Tables 1 and 2).

Comparative Example 2 The procedure of Example 1 was repeated, except that a single solvent of ethylene glycol methyl ether acetate was used as a treatment solvent instead of the immersion treatment with a hydrogenated solvent consisting of ethylene glycol methyl ether acetate-water. A photosensitive member was prepared in the same manner as in Example 1, and the electrostatic characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1
See 2).

Comparative Example 3 Example 2 was repeated except that a single solvent of ethylene glycol ethyl ether acetate was used as a treating solvent instead of the immersion treatment with a hydrogenated solvent consisting of ethylene glycol ethyl ether acetate-water of Example 2. A photoreceptor was prepared in the same manner as described above, and the electrostatic characteristics were evaluated in the same manner as in Example 2. The results are shown in Table 1
See 2).

Comparative Example 4 The procedure of Example 9 was repeated, except that a single solvent of ethylene glycol diacetate was used as a treating solvent instead of the immersion treatment with a hydrogenated solvent consisting of ethylene glycol diacetate-water. A photoreceptor was prepared in the same manner, and the electrostatic characteristics were evaluated in the same manner as in Example 9. The results are shown in (Tables 1 and 2).

(Comparative Example 5) Instead of the immersion treatment with a hydrogenated solvent consisting of γ-butyrolactone-water in Example 10,
A photoconductor was prepared in the same manner as in Example 10, except that a single solvent of γ-butyrolactone was used as the processing solvent, and the electrostatic properties were evaluated in the same manner as in Example 10. The results are shown in (Tables 1 and 2).

[0054]

[Table 1]

[0055]

[Table 2]

From the above results, the laminated electrophotographic photosensitive member of the present invention (Example) is more sensitive to long-wavelength light such as a semiconductor laser than the conventional laminated electrophotographic photosensitive member (Comparative Example). It showed good sensitivity, and it was confirmed that the sensitivity and the repetition stability of the charging property were improved.

[0057]

As described above, according to the laminated electrophotographic photoreceptor of the present invention, the oxotitanium phthalocyanine vapor-deposited film has excellent sensitivity to semiconductor laser light because of its unique crystal structure. Thus, since the charge generation layer has less carrier trapping and recombination, excellent sensitivity and chargeability can be obtained, and a photoreceptor having excellent repetition stability thereof can be obtained. Therefore, it is possible to provide a photoconductor capable of forming a high-quality image for a long time.

According to the method of the present invention, the laminated electrophotographic photoreceptor of the present invention can be efficiently, rationally and stably manufactured.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically illustrating a configuration of a laminated electrophotographic photoconductor according to an embodiment of the present invention.

FIG. 2 is a diagram showing a change in an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film which has been immersed in a hydrogenated solvent consisting of ethylene glycol methyl ether acetate-water in Example 1 of the present invention. 2) shows an absorption spectrum before the immersion treatment, and FIG. 2B shows an absorption spectrum after the immersion treatment.

FIG. 3 is a diagram showing an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after immersion treatment with a hydrogenated solvent composed of ethylene glycol ethyl ether acetate-water in Example 2 of the present invention.

FIG. 4 is a diagram showing an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after immersion treatment with a hydrogenation solvent composed of propylene glycol methyl ether acetate-water in Example 3 of the present invention.

FIG. 5 is a diagram showing an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after immersion treatment with a hydrogenation solvent composed of propylene glycol ethyl ether acetate-water in Example 4 of the present invention.

FIG. 6 is a diagram showing an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after immersion treatment with a hydrogenated solvent composed of ethylene glycol diacetate-water in Example 5 of the present invention.

FIG. 7 is a diagram showing an absorption spectrum of an oxotitanium phthalocyanine vapor-deposited film after immersion treatment with a hydrogenation solvent composed of γ-butyrolactone-water in Example 6 of the present invention.

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G03G 5/082 G03G 5/082 (72) Inventor Hitoshi Hisada 1006 Kazuma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (14)

[Claims] 1. A laminated electrophotographic photoconductor in which at least a charge generation layer and a charge transport layer are laminated on a conductive support, wherein the charge generation layer is formed by depositing an oxotitanium phthalocyanine vapor-deposited film with an alkylene Glycol alkyl ether acetate-water, alkylene glycol diacetate-water, and γ-butyrolactone-water for lamination type electrophotography characterized by being treated by immersion in a hydrogenation solvent containing at least one compound selected from water. Photoconductor. 2. The laminated electrophotographic photoconductor according to claim 1, wherein the alkylene group of the alkylene glycol alkyl ether acetate is at least one organic group selected from an ethylene group, a propylene group and a butylene group. 3. The laminated electrophotographic photoconductor according to claim 1, wherein the alkyl group of the alkylene glycol alkyl ether acetate is at least one organic group selected from a methyl group and an ethyl group. 4. The alkylene glycol diacetate according to claim 1, wherein the alkylene group is at least one organic group selected from an ethylene group, a propylene group and a butylene group.
5. The photoconductor for electrophotographic lamination according to item 1. 5. The charge transport layer is formed by applying a coating solution obtained by dissolving at least a charge transport agent and a resin binder in toluene or chloroform on the charge generation layer. 5. The photoconductor for electrophotographic lamination according to any one of 4. 6. A charge-transporting agent comprising 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl)
6. The laminated electrophotographic photoconductor according to claim 5, which is a mixture with -4,4-diphenyl-1,3-butadiene. 7. The photoconductor according to claim 5, wherein the charge transporting agent is 4-N, N-diphenylamino-α-phenylstilbene. 8. A method for producing a laminated electrophotographic photoreceptor, comprising laminating at least a charge generation layer and a charge transport layer on a conductive support, wherein oxotitanium phthalocyanine is deposited on the support, The obtained oxotitanium phthalocyanine deposited film is immersed in a hydrogenated solvent containing at least one compound selected from alkylene glycol alkyl ether acetate-water, alkylene glycol diacetate-water, and γ-butyrolactone-water to generate electric charge. A method for producing a laminated electrophotographic photoreceptor, characterized by comprising a layer. 9. The method according to claim 8, wherein the alkylene group of the alkylene glycol alkyl ether acetate is at least one organic group selected from an ethylene group, a propylene group and a butylene group. . 10. The method according to claim 8, wherein the alkyl group of the alkylene glycol alkyl ether acetate is at least one organic group selected from a methyl group and an ethyl group. 11. The method according to claim 8, wherein the alkylene group of the alkylene glycol diacetate is at least one organic group selected from an ethylene group, a propylene group and a butylene group. 12. The charge transport layer according to claim 8, wherein the charge generation layer is formed by applying a coating solution obtained by dissolving at least a charge transport agent and a resin binder in toluene or chloroform on the charge generation layer. 3. The method for producing a laminated electrophotographic photoreceptor according to item 1. 13. A charge transport agent comprising 2-methyl-4-dibenzylaminobenzaldehyde-N, N-diphenylhydrazone and 1,1-bis (p-diethylaminophenyl) -4,4-diphenyl-1,3- The method for producing a laminated electrophotographic photoreceptor according to claim 8, which is a mixture with butadiene. 14. The method according to claim 8, wherein the charge transporting agent is 4-N, N-diphenylamino-α-phenylstilbene.