JPS58140752A - Manufacture of electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain a good image even in high humidity, by coating a photoconductive layer formed on a conductive substrate with a coating liquid contg. a specified org. metal compd. and water to form an interlayer. CONSTITUTION:A photoconductive layer 3 formed on a conductive substrate 4 is coated with a coating liquid contg. a specified org. metal compd. represented by the formula R'xM(RO)y and water to form an interlayer 2. It plays roles as a barrier layer and further, an adhesive layer between a protective layer 1 and the layer 3. As said compd., tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. are embodied, This electrophotographic receptor is obtained by forming the photoconductive layer 3 of selenium or the like directly or interposing a barrier layer or a blocking layer on the conductive substrate 4, coating the layer 3 with a coating soln. obtd. by dissolving said compd. in a proper amt. of water and a solvent, drying it in the air, further coating this dried film with a coating liq. obtd. by dispersing a metal oxide and a binder resin in a solvent, and drying to form a protective layer 1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for constructing a photoreceptor for electrophotography, and more particularly, to an improvement in a method for constructing a photoreceptor for electrophotography, and more specifically, a protective layer KI provided on the surface of a photoconductive layer. ! Contains a certain organic compound or has an average particle size of 0.3a
The present invention relates to a method for manufacturing an electrophotographic photoreceptor in which high image quality can be obtained by dispersing metal oxides of m or less.

Many photoreceptors used in electrophotography including processes such as charging, exposure, and photoreceptor have been put into practical use. In order to make these photoreceptors compatible with their electrical and optical properties and mechanical properties, or to further improve and stabilize these properties, in some cases, it is necessary to improve In order to improve the characteristics, it has been proposed to provide a surface layer on the surface of the photoreceptor.

One of these surface layers is called a protective layer, and for example, a thin resin film is provided on the surface of the photoreceptor, and it is used for charging and image exposure (
A-image formation is performed using the Carlson process). However, when a photoreceptor provided with such a film-holding layer is used, a high residual potential and a large cycle increase are often observed. This high 9 residual potential and its cycle increase can be considerably improved by making the protective layer thinner, but this is not a substantial improvement as it is accompanied by a low F of the mechanical strength of the film. On the other hand, as another surface layer, a resin with high electrical resistance called an insulating layer is provided on the surface of the photoreceptor. ) to form a latent image. However, these methods are more complex as a whole, as they involve an increase in the number of charging processes compared to the Carlnon process, and are disadvantageous in terms of reliability of the entire device.

The present invention relates to a photoreceptor provided with the former protective layer, and more particularly, to a method for manufacturing a photoreceptor in which formation of an a-image can be performed by a so-called Carlson process without using a special a-image forming process. . The present applicant has previously proposed a low resistance protective layer as a solution to the above-mentioned drawbacks (for example, Japanese Patent Application No. 54-42118, Japanese Patent Application No. 54-65671, Japanese Patent Application No. 54-65672 and Japanese Patent Application No. 54-65672). 54
-65673). By providing the low-resistance protective layer proposed by these methods, high-quality *
*However, it has been found that depending on the type of photosensitive layer, the charging performance of the entire photoreceptor may decrease, resulting in the inability to obtain images with sufficient contrast. . Therefore, the present applicant has proposed an electrophotographic photoreceptor in which an intermediate layer containing an organic metal compound as a main component is provided between a photosensitive layer and a protective layer as a photoreceptor that has improved these problems ( Special application 1984-1
17101q, 5656-1l7110, 56-1
594209). However, if these intermediate layers are directly provided on the photosensitive layer, good me can be obtained at low humidity, but the resolution sometimes decreases at high humidity. One is the humidity dependence of the electrical resistance of the intermediate layer, which is thought to be due to increased conductivity due to the influence of moisture at high temperatures.

An object of the present invention is to provide a method for manufacturing an electrophotographic photoreceptor that does not have the above-mentioned drawbacks, and in particular, to provide an electrophotographic photoreceptor that provides good images even at high humidity.

The object of the present invention is to form a photoconductive layer on a conductive support, and then apply the general formula (I) (t'xM(ito
), ), (1) [where M is Si, TI,
Zr, AA, or V, k' is an alkyl group having 1 to 17 carbon atoms, or an aryl group, k is an alkyl group having 1 to 6 carbon atoms, or an aryl group, X is O or an integer of 1 to 3, y represents an integer of 1 to 4, and dew represents an integer of 1 to 5. ] Achieved by a method for manufacturing an electrophotographic photoreceptor, which comprises forming an intermediate layer by applying a coating solution containing an organic metal compound represented by the formula and water, and then forming a protective layer on the intermediate layer. can do.

The structure of the electrophotographic photoreceptor obtained by the method of the present invention is as follows.
As shown in the figure. In the figure, 1 contains an organic polymer compound added with an appropriate organic compound, or has an average particle size of 0.3 μm.
A low-resistance protective layer made of an organic polymer compound in which metals or metal oxides are dispersed, 2 is an intermediate layer, 3 is a photosensitive layer 1
5.4 is a conductive support.

Suitable organic compounds for use in the protective layer 1 include metallocenes and compounds having at least one metallocene skeleton in their molecular structure.

In addition, the metal φ can be any metal or metal oxide powder as long as it has a specific volume resistivity of 10110.1 or less and an average particle size of 0.3 μm or less.
can be used. For example, gold, silver, aluminum,
Examples include metals such as iron, steel, and nickel, and metal oxides such as zinc oxide, titanium oxide, tin oxide, bismuth oxide, indium oxide, and antimony oxide. At this time, several types of metals and metal oxides may be used in combination.

Particularly preferred is a powder containing tin oxide and antimony oxide and having an average particle size of 0.15 μF or less.

The organic polymer compound (binding side) used in the protective layer is preferably one that is substantially transparent to visible light and has excellent electrical insulation, mechanical strength, and adhesiveness. For example, polyester resin, polycarbonate resin, polyurethane resin, epoxy resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, silicone resin, alkyd resin, polyvinyl chloride resin, cyclized butadiene rubber, fluororesin, etc. can be used. When solvent resistance of the protective layer is required, it is desirable to use a curable resin.

The composition ratio of the binder resin and organic compound in the protective layer, or the composition ratio of metal or one metal compound, varies depending on the combination of materials, but the organic compound is 5 to 100 parts by weight per 100 parts by weight of the binder resin. For metals or metal oxides, it is used in an amount of 5 to 500 parts by weight, preferably 5 to 100 parts by weight. The thickness of the protective layer is 1 to 30μ as necessary.
It can be set between

In addition to its role as a barrier layer, the intermediate layer 2 can also function as an adhesive layer between the protective layer and the photosensitive layer. In the above formula (I) representing the compound used in the intermediate layer, carbon number 1
~17 alkyl groups include methyl group, ethyl group, i
-propyl group, n-propyl group, 1-butyl group, n-butyl group, decyl group, dobucle group, cetyl group, stearyl group and the like. In addition, examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, I-propyl group, n
-propyl group, i-butyl group, a-butyl group, etc. Examples of the aryl group R' and the mouse include a benzyl group and a phenyl group.

Examples of the compound of general formula (I) include tetramethoxysilane, tetraethoxytitanium, tetrabutoxysilane, tetrabutoxysilane, te, um, 87ki, /, /u2, te, ram, di, oxy.

Silane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, jetoxydimethylsilane/, triethoxymethylsilane, ethoxytrimethylsilane, jetoxydiethylsilane, triethoxyethylsilane, phenoxytrimethylsilane , trimethoxyphenylsilane, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrabutoxytitanium dimer, jetoxydibenzyltitanium, tetraethoxysilconium, tetrabutoxyzirconium, tetrabutoxyzirconium, triethoxyvanadium, tripropolyacium , tributoxyaluminum, methoxydimethylaluminum, ethoxydiethylaluminum, triethoxyvanadium, triethoxyvanadium, and triethoxyvanadium.

These compounds forming the intermediate layer can be used alone or as a mixture of two or more. When a coating solution containing these compounds is applied onto the photosensitive layer 3 by an appropriate method such as gray coating, dip coating, knife coating, or roll coating to form the intermediate layer 112, it is not necessary to heat it at a high temperature after coating. and showed a large humidity dependence,
Although there were major practical limitations, the present inventor discovered that it is possible to form a fully functional intermediate layer on any photosensitive layer without any heat treatment (i.e., by simply air drying). .

To explain the formation method, first, a photoconductive layer of selenium or the like is provided on a conductive support directly or via a barrier layer or a protective layer or a king layer. Next, a coating solution in which an organometallic compound is dissolved in an appropriate amount of water and a solvent is applied onto the photoconductive layer and air-dried. A coating solution containing a metal oxide and a binder resin dispersed in a solvent is applied onto this dried film and dried to form a coating of 11 Nm. At this time, a catalyst may be added to the intermediate layer coating solution. The amount of water or catalyst that is added has a great effect on the function of the finished intermediate layer (it is necessary to use the optimum amount for the combination of solid materials, but the solid content of the intermediate layer material in terms of weight ratio The same (0,
Preferably, a catalyst in the range 5 to 0.001 is used. The catalysts used here are higher fatty acids, resin acids, naphthi 7
fllfK (1) Refers to salts of manganese, cobalt, aluminum, steel, zinc, chromium, calcium, etc.

By this method, it is possible to obtain a photoreceptor that produces images as good even in high humidity as in low humidity, and it is also possible to provide an intermediate layer for photosensitive layers that conventionally suffer from crystallization or thermal decomposition when heated at high temperatures. This greatly expanded the degree of freedom in selecting the photosensitive layer.

Hereinafter, the effects of the present invention will be explained using examples. In each example, the intermediate layer and the ring 11 layer were not subjected to any heat treatment.

Example Aa! was deposited to a thickness of 50 μm on an I M substrate by a conventional vapor deposition method. An intermediate layer solution and a protective layer solution having the following composition were sequentially applied onto the S@3 photosensitive layer and air-dried to obtain a comparative electrophotographic photoreceptor.

Intermediate layer liquid: Methyl-trimethoxy77ran (trade name: IBM-13,
(Manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts by weight Tetrabutoxyzirconate (Product name: ZA-60, manufactured by Matsumoto Henmen Co., Ltd.) 10 parts by weight Butanol soo Parts by weight Ingropanol 50 parts by weight Protective layer liquid Nidimethyl 7 Erosene 22 Part by weight Folyarylate (Product name: U-polyff-, manufactured by Unitika)
78 parts by weight Dichloromethane 10001 t parts The composition of the intermediate layer liquid used to form the electrophotographic photoreceptor for comparison was changed as shown below, and the other parts were made in the same manner as in (2). ) was obtained.

Intermediate layer liquid: Methylute-su-methoxysilane (product name 2KBM-1
3. Shin-Etsu Chemical Co., Ltd. 11) 10 tt parts water 5 parts cobal naphthenate) 11 The thickness of #@ was 0.3 μm and 10 μm, respectively. The resolution of images obtained by both photoreceptors was adjusted under low humidity (30% RI).
A comparison was made with I) after sufficient humidity control under high temperature (85 inches RH), and both fsA and B gave a good image with a resolution of 8/■ under low humidity, but under high humidity, ■ had a remarkable 3467 haze. Although the resolution showed a decrease, the resolution of (2) remained unchanged at 8 Lp/■.

Example 2 A photoreceptor (C) was produced in exactly the same manner as in (6) except that the composition of the intermediate layer liquid used to form the photoreceptor (width) in Example 1 was changed to the following.

Intermediate layer liquid: Tetraethoxysilane 5 parts by weight Tetra n-butoxyzirconate 10 parts by weight Tetraisoglobil titanate 5 parts by weight Water 1.5 parts Cobalt naphthenate Tsuru-Ptanol 350 parts by weight was applied to this photoreceptor (C) in the same manner as in Example 1. IIJf
When we conducted a resolution test at i and low mT, the resolution was 8 Lp/ under high temperature and low humidity, similar to the photoreceptor width).
It gave a good image of VM or higher.

Example 3 A photoreceptor (b) was obtained in exactly the same manner as in (6) except that the intermediate layer liquid used to form the photoreceptor (width) in Example 1 was changed to the following composition.

Intermediate layer liquid: Tetra-Globilzirconate 4 parts by weight Phenyl
Trimethokilan 10-fold panadil ethylate
1 part by weight Tetraethoxysilane 3 parts by weight Magnesium methoxide 1 part by weight Cobalt heptate 1 part by weight Water 10 parts by weight Imppanol 500 parts by weight This photoreceptor (2) was filled with ml medium as in Example 1. When tested, it showed good results with a resolution of 8 or more/gm under high humidity and low humidity, similar to the photoreceptor (IN).

Example 4 The following intermediate layer liquid and protective layer liquid were applied and dried on a two-layer photosensitive layer consisting of a Se (50 μm thick) vapor deposited layer and a Se-Te alloy vapor deposited layer (2 μm thick) provided on an M back conductive substrate. Then, photoreceptors (6) each having a thickness of 0.3 μm and 110 μm were obtained.

Intermediate layer liquid: Methyltrimethoxysilane 12 parts by weight Butyl titanate dimer (product name: ORGATIX TA-22, Matsumoto Koshosha II) 8 parts Tetra n-butyl zirconate 5 parts by weight Water 7 parts by weight Ingropanol 150 Part by weight 3-butanol 150 parts by weight Holding layer liquid: Polyacrylic urethane resin (trade name Nirethane 4000
, manufactured by Kansai Paint) 70 parts by weight of tin oxide/antimony oxide fine powder (average particle size ~01μ) 30 parts by weight of thinner (trade name: Niretan Thinner, manufactured by Kansai Paint)
70 parts by weight hardening agent (trade name Nirethane hardening agent, manufactured by Kansai Paint) 10
Part by weight When a resolution test was conducted on this photoreceptor (6) in the same manner as in Example 1, the resolution was 8 in both high and low humidity.
A good s-image of 4P/■ or more was obtained.

[Brief explanation of the drawing]

The drawings represent the structure of an electrophotographic photoreceptor obtained by the method of the present invention. Symbols in the figure: 1...Low resistance protective layer; 2...Intermediate layer; 3...Photoconductive layer; 4...Electroconductive support. Representative Patent Attorney (8107) Kiyotaka Sasaki (and 3 others)

Claims (1)

[Claims] After forming a photoconductive layer on a conductive support, a compound of the general formula (summer) (1'!M(1G)A Ig (I) [in the formula, M
T! Si, T1. Zr, At or V,
Nezumi'flea: 1 alkyl group having 1 to 17 carbon atoms, or aryl group, Nezumi: alkyl group having 1 to 6 carbon atoms, or aryl group,
is 0 or an integer from 1 to 3, ytt is an integer from 1 to 4, and ytt is an integer from 1 to 4.
An electronic device characterized in that an intermediate layer is formed by applying a coating liquid containing an organometallic compound represented by an integer of 5 and water, and then a protective layer is formed on the intermediate layer. A method for manufacturing a photographic photoreceptor.