JPS62273549A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the titled body having a very small dark attenuation of the electrostatic charge potential by constituting a photoconductive layer from an n-type semiconductor which comprises an amorphous silicon contg. hydrogen atom as a main component, and also phosphorous atom as an impurity, and by constituting an intermediate layer from a dried curing material of a solution contg. at least one kind of an org. zirconium compd. CONSTITUTION:The intermediate layer is laminated on a conductive substrate, and the conductive layer composed of the amorphous silicon is coated on the intermediate layer. The dried curing material of the solution contg. at least one kind of the org. zirconium compd. is used as the intermediate layer. The n-type semiconductor which contains the amorphous silicon contg. hydrogen atom as the main component, and also contains the phosphorous atom and at least one kind of carbon atom, nitrogen atom and oxygen atom as an impurity is used the photoconductive layer. The further preferable org. zirconium compd. is exemplified by a zirconium complex and a zirconium alkoxide. Thus, the high mechanical strength, the high durability, the high heat- resisting property and the high photosensitivity of the titled body are maintained, and the high electric charge holding power of the titled body is obtd., without being affected by the surroundings of an outside and the number of using, thereby obtaining the picture image having excellent quality.

Description

DETAILED DESCRIPTION OF THE INVENTION 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor using amorphous silicon for the frame and photosensitive layer.

In the conventional electrophotographic method, a photoreceptor is charged and an electrostatic layer 1' is formed by image exposure.
This is a method of forming a latent image, developing this latent image with a developer containing toner, and then transferring and fixing the toner image onto transfer paper to obtain a copy. The basic structure of a photosensitive tube used in this electrophotographic method is that a photosensitive layer is laminated on a conductive substrate. Conventionally, the materials constituting the photosensitive material 1 have been selenium or selenium alloys, inorganic materials such as cadmium sulfide, zinc oxide, photosensitive materials, or polyvinylcarbazole,
Photosensitive materials containing trinitrofluorenone, bisazo pigments, phthalocyanine, pyrazoline, hydrazone and the like are known, and photosensitive layers are used in the form of TL or laminated layers.

Problems to be Solved by the Invention However, these conventionally used photosensitive layers have problems in durability, heat resistance, photosensitivity, etc. that still need to be solved.

In recent years, photoreceptors using amorphous silicon as the photosensitive layer have been known, and various attempts have been made to improve them. This photoreceptor using amorphous silicon has an amorphous film of silicon formed on a conductive substrate using silane (SiH4) gas using a glow discharge decomposition method. It incorporates hydrogen and Oji and exhibits photoconductivity. This amorphous silicon photoreceptor has a photosensitive layer that has a high surface hardness and is resistant to scratches, is resistant to abrasion, has high heat resistance, and has excellent mechanical strength. Furthermore, amorphous silicon has a wide spectral sensitivity range and has excellent photosensitivity, such as high photosensitivity. However, on the other hand, photoreceptors using amorphous silicon have the disadvantage that dark decay is large and a sufficient charging potential cannot be obtained even when charged. That is, when an amorphous silicon photoreceptor is charged, imagewise exposed to form an electrostatic latent image, and then developed, the surface charge on the photoreceptor is exposed to light during the imagewise exposure process or the development process. Even the charge in the areas that were not exposed to irradiation is attenuated, making it impossible to obtain the charging potential necessary for development.This attenuation of the charging potential easily changes depending on the influence of environmental conditions, especially in high temperature and high humidity environments. The potential decreases significantly.Furthermore, when an amorphous silicon photoconductor is used repeatedly, the charging potential gradually decreases.It is difficult to make copies using a photoconductor with such a large Iff decay in the charging potential. When created, the image!1rAa degree is low, and
This results in a copy with poor reproduction of halftones.

An object of the present invention is to provide an electrophotographic photoreceptor that eliminates the above-mentioned drawbacks of photoreceptors using amorphous silicon.

Furthermore, the object of the present invention is to use amorphous silicon, and
An object of the present invention is to provide an electrophotographic photoreceptor in which the dark decay of the charged potential is extremely small.

Another object of the present invention is to provide an electrophotographic photoreceptor whose charging characteristics are not affected by changes in the external environment.

Another object of the present invention is to provide an electrophotographic photoreceptor that maintains excellent image quality even after repeated use.

A further object of the present invention is to provide an electrophotographic photoreceptor having excellent electrophotographic properties such as mechanical strength, durability, heat resistance, and photosensitivity.

Means for Solving the Problems As a result of extensive research, the present inventor deposited an intermediate layer on a conductive substrate, coated it with a photoconductive layer made of amorphous silicon, and It has been found that the above object can be achieved by using, as the intermediate layer, a dried and cured product of a solution containing at least one type of organic zirconium compound. The photoconductive layer is mainly made of amorphous silicon containing hydrogen atoms, contains phosphorus atoms as impurities, and further contains at least one of carbon atoms, nitrogen atoms, and oxygen atoms.
An n-type semiconductor containing a type of semiconductor is used.

Thus, according to the present invention, in an electrophotographic photoreceptor in which an intermediate layer and a photoconductive layer are successively laminated on a conductive substrate, the photoconductive layer is made essentially of amorphous silicon containing hydrogen atoms. Drying and curing of a solution comprising an n-type semiconductor containing a phosphorus atom as an impurity and further containing at least one type of carbon atom, nitrogen atom, or oxygen atom, the intermediate layer containing at least one type of organic zirconium compound. An electrophotographic photoreceptor is provided.

Although various organic zirconium compounds can be used to form the intermediate layer of the electrophotographic photoreceptor of the present invention, particularly preferred are zirconium complexes and zirconium alkoxides. Preferred examples of these include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tryptoquine acetylacetonate, zirconium trifluoroacetylacetonate, zirconium tetra-n-propoxide, zirconium tetra-iso-propoxide. Examples include zirconium-n-butoxide, zirconium isobutoxide, and the like.

In order to obtain the electrophotographic photoreceptor of the present invention, a solution of one or more of the above organic zirconium compounds dissolved in a suitable solvent is coated. Further, at this time, a solution obtained by mixing these organic zirconium compounds with an organic silicon compound may be used. Compounds generally called silane coupling agents are suitable as the organosilicon compound, such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and T-glycidoxypropyltrimethoxine. Ran, r-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) r-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxy Silane, r-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
Examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmonomethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy/silane, and monophenyltrimethoxysilane. When such a 7-run coupling agent is mixed and used, it is preferable that the amount of the plan coupling agent is 5 to 50% based on the total solid weight.

Thus, a solution containing an organozirconium compound and optionally an organosilicon compound is applied onto a conductive substrate by methods such as spray coating, dip coating, knife coating or roll coating, dried and cured, and then applied. The electrophotographic photoreceptor of the present invention can be manufactured by laminating a photoconductive layer on the photoreceptor.

The drying and curing temperature can be set at any temperature between 100 and 400°C. The thickness of the intermediate layer finally obtained can also be set arbitrarily, but 0.1 to 10 μm is suitable.

The photoconductive layer mainly composed of amorphous silicon is SiH3+2
Using one type of hydrogen silicon gas such as tlI+, 513H@, 514H1°, or a mixture thereof as a raw material, it is formed on the intermediate 1 by a method such as a glow discharge method, a sputtering method, an ion blasting method, or a vacuum evaporation method.

Among them, Bladder 7 CV D (Chemical Va
por Deposition) method, silane (
Sift, ) Method of decomposing gas, etc. by glow discharge (
Glow discharge method) is preferred from the viewpoint of controlling the hydrogen content in the film.

Further, in this case, in order to more efficiently contain hydrogen, hydrogen (H2) gas may be separately introduced into the plasma CVD apparatus at the same time as silane gas or the like. Furthermore, from the viewpoint of film growth rate, it is preferable to use SiH4,5i2L.

The photoconductive layer of the electrophotographic photoreceptor of the present invention is made of an n-type semiconductor mainly composed of amorphous silicon containing hydrogen atoms and containing phosphorus atoms as impurities;
The inclusion of atoms containing at least one of carbon atoms, nitrogen atoms, and oxygen atoms increases the dark resistance of the photosensitive layer, increases the photosensitivity, and further increases the chargeability (unit: Phosphine (PH) gas is preferably used as a raw material for adding phosphorus (P) atoms to the amorphous silicon photosensitive layer from the viewpoint of increasing the charge potential per film thickness. In this case, the amount of P atoms added is 0.01~t o
It is on the order of Oppm.

Furthermore, it is also possible to add an element such as germanium (Ge) to the photoconductive layer film for the purpose of increasing the sensitivity of the photoreceptor in the long wavelength region. Further, by adding halogen atoms, it is also possible to increase the dark resistance.

Thus, in order to prepare the photoconductive layer of the photoreceptor for electrophotography of the present invention, silicon hydride gas as a soil raw material, and hydrogen gas as desired, are used in a plasma CVD apparatus together with these gases. , a gaseous compound containing necessary elements may be introduced to perform glow discharge decomposition. As mentioned above, effective discharge conditions for forming a photoconductive layer made of amorphous silicon by plasma c V D 71 include, for example, in the case of AC discharge, the frequency is usually 0.1 to 30 Mtlz, and the vacuum during discharge is degree is 0.1 to 5 Torr, substrate heating temperature is 10
The temperature is 0 to 400°C. Therefore, the film thickness of the photoconductive layer mainly composed of amorphous silicon is 1 to 100 μm, particularly 10 to 5 μm.
It is preferable to set it to 0 μm.

As the conductive substrate, a metal such as aluminum, nickel, chromium, stainless steel, or brass, a plastic sheet or glass having a conductive film, or paper treated to be conductive can be used. Moreover, the shape of the conductive substrate can be any shape such as a cylindrical shape, a flat plate shape, an endless belt shape, or the like.

EXAMPLES Next, the electrophotographic photoreceptor of the present invention will be further explained with reference to comparative examples and examples of the present invention.

Comparative Example 1: A cylindrical Aβ substrate was installed at a predetermined position in a reaction chamber of a capacitively coupled plasma CVD apparatus, the substrate temperature was maintained at a predetermined temperature of 250°C, and 100% silane (Si) was placed in the reaction chamber.
H,) 120CG/min of gas, 300p of hydrogen dilution
pm Phosphine (PH3) gas at 3Qcc/min and ethylene (C2H,) gas at 15cc/min.

Furthermore, 100% hydrogen (N2) gas was introduced at a rate of 75 CC per minute to maintain an internal pressure of 0.5 Torr in the reaction tank, and then a high frequency power of 13.57 M) Iz was applied.
A glow discharge was generated and the output of the high frequency power source was maintained at 85W. In this way, a photoreceptor having a 25 μm thick photoconductive layer made of an n-type semiconductor mainly composed of amorphous silicon, containing phosphorus atoms as an impurity, and further containing hydrogen and carbon, on a cylindrical Af substrate. I got it.

When the photoreceptor thus obtained was placed in a copying machine and the image quality was evaluated using a negative corona charging method, an image density that was acceptable for practical use was not obtained.

Example 1: A solution consisting of 1 part by weight of zirconium acetylacetone, 50 parts by weight of methyl alcohol, and 20 parts by weight of n-butyl alcohol was applied by dip coating onto a cylindrical substrate having the same shape as Comparative Example 1, and heated at 250°C. Dry in the oven for 2 hours and get 0.
A 2 μm thick intermediate layer was provided.

Next, on this intermediate layer, a photoconductive layer mainly made of amorphous silicon having the same content as in Comparative Example 1 was provided by the same method as in Comparative Example 1, and with almost the same thickness as in Comparative Example 1.

The photoconductive layer thus obtained had properties similar to ceramics, and had the same surface hardness, abrasion resistance, and heat resistance as amorphous silicon.

In this way, the photoreceptor that had been tampered with was placed in a copying machine and the image quality was evaluated using a negative corona charging method. Although the operation was repeated 50,000 times, no decrease in image density was observed.

Comparative Example 2: A cylindrical A f substrate was installed at a predetermined position in the reaction chamber of a capacitively coupled plasma CVD apparatus, the substrate temperature was maintained at a predetermined temperature of 250°C, and 100% 7 runs (S
iH,) gas at 12 Qcc per minute, 300 p of hydrogen dilution
pm Phosphine (PL) gas was introduced at 39cc/min, 100% nitrogen (N2) gas at 9Qcc/min, and 100% hydrogen (N2) gas at IQcc/min. After maintaining at 13
．． A high frequency power of 5614 Hz was applied to generate a glow discharge, and the output of the high frequency power source was maintained at 80 Wi:. In this way, a thickness of 2
A photoreceptor was obtained having a photoconductive layer having a thickness of 5 .mu.m and consisting of an n-type semiconductor mainly composed of amorphous silicon and containing phosphorus as impurities, as well as hydrogen and nitrogen.

When the photoreceptor thus obtained was placed in a copying machine and the image quality was evaluated using a negative corona charging method, an image density that could withstand practical use was not obtained.

Example 2: On a cylindrical Af substrate having the same shape as Comparative Example 2, 1 part by weight of zirconium tetrabutoxide and 10 parts by weight of ethyl alcohol were added.
A solution consisting of 0 parts by weight was applied by dip coating and dried in an oven at 250° C. for 2 hours to provide an intermediate layer with a thickness of 0.2 μm. next,
Comparative Example 2 was applied onto this intermediate layer by the same method as Comparative Example 2.
A photoconductive layer mainly composed of amorphous silicon having the same content as in Comparative Example 2 was provided with approximately the same thickness as Comparative Example 2.

When the photoreceptor thus obtained was placed in a copying machine and the image quality was evaluated using a negative corona charging method, an image density that was acceptable for practical use was obtained at the initial stage. Further, although the copying operation was repeated 50,000 times, no decrease in image density was observed.

Comparative Example 3: A cylindrical Aβ group was installed at a predetermined position in the reaction chamber of a capacitively coupled plasma CVD apparatus, the substrate temperature was maintained at a predetermined temperature of 250°C, and 100% silane (Si) was placed in the reaction chamber.
H,) gas per minute at 12 Qcc, 300pp of hydrogen dilution
m phosphine (Pl'13) gas at 39cc per minute
, and 100% oxygen (0□) gas at 1.9 c/min.
c. Furthermore, 100% hydrogen (H2) gas was introduced at a rate of 89 cc per minute to maintain an internal pressure of Q, 5 Torr in the reaction tank, and then 13.56 MHz high frequency power was applied to generate a glow discharge and high frequency The output of the power supply was maintained at 85W. In this way, on the cylindrical Aj2 substrate, a thickness of 2
A photoreceptor having a photoconductive layer having a thickness of 5 μm and consisting of an n-type semiconductor mainly composed of amorphous silicon and containing phosphorus as impurities and hydrogen and oxygen was obtained.

When the photoreceptor thus prepared was placed in a copying machine and the image quality was evaluated using a negative corona charging method, no image capable of withstanding practical use was obtained.

Example 3: A solution consisting of 1 part by weight of zirconium tetrabutoxide, 1 part by weight of methyltrimethoxysilane, 100 parts by weight of ethyl alcohol, and 100 parts by weight of isopropyl alcohol was immersed onto a cylindrical Aβ substrate having the same shape as in Comparative Example 3. It was coated and dried in an oven at 250° C. for 2 hours to form an intermediate layer with a thickness of 0.1 μm.

Next, on this intermediate layer, a photoconductive layer mainly composed of amorphous silicon having the same contents as in Comparative Example 3 was provided by the same method as in Comparative Example 3 and having almost the same thickness as in Comparative Example 3.

When the photoreceptor thus prepared was placed in a copying machine and the image quality was evaluated using a negative corona charging method, an image density of no problem for practical use was given at the initial stage. Further, although the copying operation was repeated 50,000 times, no reduction in image density was observed.

Effects of the Invention The electrophotographic photoreceptor of the present invention retains the excellent properties of a photoreceptor made of amorphous silicon, such as high mechanical strength, high durability, high heat resistance, and high photosensitivity, and is also resistant to the external environment. It has a high charge retention ability regardless of the number of times it is used or the number of times it is used, and can produce images of excellent quality.

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor comprising an intermediate layer and a photoconductive layer sequentially laminated on a conductive substrate, wherein the photoconductive layer is mainly composed of amorphous silicon containing hydrogen atoms as an impurity. The intermediate layer is made of an n-type semiconductor containing phosphorus atoms, and further contains at least one of carbon atoms, nitrogen atoms, and oxygen atoms, and the intermediate layer contains at least one organic zirconium compound.
1. A photoreceptor for electrophotography, characterized in that it is made of a dried and cured product of a solution containing various types of photoreceptors.