JPS5829510B2 - Seiden Fuchsia Insatsuban - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses an aluminum film mainly as a conductive layer, and an inorganic substance containing Se as a main component and exhibiting photoconductivity in an amorphous state is vacuum-deposited thereon. In copy printing plates, it prevents crystallization and deterioration of the photoconductive layer,
Accordingly, it relates to a method for improving the photoconductive properties of said photoconductive layer.

Another purpose is to improve the adhesive strength between the photoconductive layer and the aluminum film.

In addition, another purpose is to form the photoconductive layer and the conductive layer (leak layer).
The purpose is to improve the contact with the metal, that is, the mobility of the charges.

So-called electrostatographic printing plates, i.e. on a suitable conductive layer,
A layer of photoconductive material is provided, and the photoconductive layer is sensitive to light and creates a latent image with an electrostatic charge, so that colored particles (toner) are attracted to the electrostatic material and a , the toner,
In the copy printing plate that transfers (copies) to the printing material,
As the photoconductive substance, it is well known that an inorganic substance containing Se as a main component is one of the substances that currently exhibits excellent photoconductive performance.

It is also well known that Se itself and photoconductive inorganic substances containing Se as a main component exhibit excellent photoconductivity in an amorphous state.

However, the performance of the photoconductive material containing Se as the main component varies depending on the properties of the conductive layer required as the charge leak layer in the underlying layer, and therefore the selection of the conductive layer is This is an important issue in the production of electronic copy printing plates.

An aluminum film is useful as this base conductive layer, or at least as a base layer that can simultaneously serve as a conductive layer.

Examples of the aluminum film include rolled aluminum plates and foils, or plated or vacuum-deposited aluminum films.

These aluminum films have good and useful underlying conductivity for charge transfer from Se or an inorganic material containing Se as a main component, which exhibits photoconductivity in an amorphous state, to the conductive layer, that is, leakage during lightning. Although it is a metal layer, the S
e It has been found that the photoconductive layer itself is not necessarily a good layer with respect to troubles such as deterioration, such as crystallization or oxidation, which are particularly important problems.

The present invention is the result of research into improving this photoconductive layer containing Se as a main component and discovering a new and useful method.

That is, the present invention provides se or S on an aluminum film.
In an electrostatic copying printing plate formed by vacuum-depositing an inorganic substance which exhibits photoconductivity in an amorphous state and whose main component is e, Te (tellurium) is first deposited on the aluminum film at a weight average thickness of 05A. After vacuum deposition and surface deposition treatment on the aluminum film, the above-mentioned
A photoconductive electrostatic copying printing plate is produced by forming by vacuum deposition an inorganic material layer which exhibits photoconductivity in an amorphous state and mainly contains Se or Se.

In the present invention, various substrates are selected for the printing plate.

For example, various synthetic resin sheets, films, or molded bodies may be used.

Typical examples include polyester such as polyethylene terephthalate, nylon, epoxy resin, phenol resin, polyvinyl chloride, and polyolefin.

Of course, it is obvious that the invention is not limited to these examples.

Further, various metal plates or molded bodies may be used. These shapes may be plate sheets or cylindrical.

In any case, aluminum is coated thereon by vacuum evaporation, plating, etc., or a rolled plate or foil is laminated thereon.

Of course, the substrate itself may be an integrated aluminum plate or foil, or a molded body.

Alternatively, a molded body such as another metal plate or a cylinder may be used.

A particularly serious defect occurs when an inorganic substance that exhibits photoconductivity in an amorphous state consisting mainly of Se or Se as a main component is formed on these aluminum layers by vacuum evaporation. Although good photoconductivity is initially exhibited and the structure is amorphous and desirable in X-ray diffraction, over time the Se layer rapidly turns mainly gray or black, i.e. Due to crystallization and a sudden drop in photoconductivity, this deterioration in performance becomes more pronounced as the temperature and humidity increase.

Such troubles arise in the case of electrostatic copying printing plates, when the printing plate is finally developed with the above-mentioned toner,
Furthermore, since the image is fixed by heat after being transferred to the object, it is inevitable that the printing plate will be affected by the heat at least in the copying machine, and the printing life of the printing plate will be shortened accordingly. This is a matter of commercial importance as it significantly reduces the aging life and leads to a significant reduction in product value.

This rapid decline (deterioration) in the performance of photoconductive layers containing Se or Se as their main component over time is mainly due to the rapid onset of crystallization of these substances, but at the same time, oxidation that produces oxidized Se has also been observed. be done.

In any case, these changes and deteriorations of the Se layer impair its main property of photoconductivity, so in order to prevent this, various anti-aging agents and crystals are added to the Se layer at the same time. There have been proposals to add inhibitors, and of course they have some effect, but the present invention is better if these known small improving powers are used in combination, and even if they are not used together, they can be used alone. Demonstrates a sufficiently useful effect.

Specifically speaking about the differences between these prescriptions, for example,
Adding Te at the same time during Se vapor deposition, that is, 11 simultaneous vapor deposition 1', is known as one recipe for improving the performance of Se, but in the present invention, in particular, Te is added separately, Moreover, the feature is that the aluminum film, which is a conductive layer that has limited characteristics, is pretreated, and this treatment also improves the adhesion between Se and the aluminum layer. A useful effect was also discovered in that the mobility and leakage of charges from the photoconductive layer mainly composed of Se to the conductive layer were improved.

Formation of Te in the present invention is performed by vacuum evaporation, sputtering, ion blasting, etc.

In vacuum evaporation, ordinary resistance heating method, conduction heating method,
Electron beam heating method or even laser heating method may be used.

In addition, various known sputtering methods such as cathode sputtering, high frequency sputtering, and plasma sputtering are used for sputtering.

These Te deposits must be deposited in vacuum as described above.

The degree of vacuum during vacuum deposition is less than I x 10-"Torr, including the case of sputtering, since Te has a relatively high vapor pressure and can be deposited during vapor deposition even if it is not under a particularly high vacuum. If so, it is good and I
It is even better if the XI is 0-2 Torr or less.

The thickness is the density of Te alone (-6.25g/c
The thickness is calculated from the weight average thickness based on Ifl),
The depth must be between 0.5 and 300 people.

Below 05λ, the adhesion layer is too thin, and more specifically, at this thickness, it is not a uniform film, and the 11 islands of Te scattered on the aluminum layer exist too infrequently.
It is too poor to prevent modification and aging, and to improve adhesion and charge mobility.

On the other hand, if the thickness exceeds 300λ, the film becomes thick enough that Te itself finally exhibits its original property of spreading, so that the effect is rather reversed.

In this respect, it can be seen that the method of the present invention has a completely different reason and mechanism from the previously known case where Te and Se are simultaneously deposited.

In other words, in the present invention, the characteristic properties of the aluminum film itself, such as crystals of aluminum, structure, electrical properties such as potential, etc., are applied to the vacuum deposition of a thin Te film on the aluminum film. This shows that Te is utilized latently and synergistically by this process, and the upper limit thickness of a good Te thin film that can be effectively produced under the influence of the underlying A1 layer is 300. It is.

In other words, no advantageous effect is exhibited on a complete Te film alone, and in this respect, the above-mentioned known T
An example of forming a photoconductive layer by simultaneously depositing e with Se is
They also differ essentially in their mechanism of action.

The best thickness for Te is 5 to 100.

In the vacuum deposition method, both vacuum evaporation and sputtering can be effectively used, but in the case of extremely thin films, sputtering is advantageous because the thickness can be precisely controlled.

A particularly effective method is to evaporate Te without breaking the vacuum system, that is, preferably immediately after aluminum evaporation, when the aluminum layer is formed by vacuum evaporation. It is.

That is, a substrate 1 such as a base sheet unwound as shown in FIG. This is a method in which the aluminum layer 3 is deposited continuously.

The method of vacuum-depositing Te of the present invention on the AI film is based on the method previously proposed by the present inventors, in which various types of gold maple were first sputtered on a synthetic resin substrate, and then aluminum was vacuum-deposited on a conductive substrate. It can also be applied on the Al, in which case even better adhesion, mechanical durability and Se
This results in good results in terms of prevention of crystallization, improvement of photoconductive performance, smoothness of charge transfer, sharpness of image formation, etc. of the photoconductive layer containing Te as the main component. Se or a photoconductive material containing Se as a main component is formed by vacuum evaporation using various known methods.

Here, the photoconductive inorganic substance that exhibits photoconductivity in an amorphous state containing Se or Se as its main component is:
Refers to materials that exhibit photoconductivity due to the movement of electrons or holes generated by light irradiation, and those that are particularly effective are those that contribute to photoconductivity due to the greater mobility of holes. It is.

The representative one among these is Se in an amorphous state,
In addition, As, Te, etc. are added to Se, and in addition to this, TeAsSe2, As2Se3As2Te, etc.
There are also 3 etc.

The thickness of these Se layers may vary, but the thickness is generally less than 500 or more.

In this way, as shown in FIG. 2, the A1 layer 3
A thin film 5 of Te is formed thereon, and a photoconductive layer 6 containing Se as a main component is formed. Not only that, but also the good properties of the Se layer make it more effective.

The effects achieved by the method of the present invention are extremely useful, especially in improving the performance of photoconductive layers containing Se as a main component.

In general, Se or Se-based photoconductors crystallize in a short period of time at 87°C to 90°C and lose photoconductivity, but at 45°C to 60'C they crystallize under various conditions. There is a big difference in the deterioration lifespan.

This is a significant difference because in an actual copying machine, this temperature is close to the temperature at which the printing plate is subjected to thermal fixing of toner, and an improvement in this would be a very useful advantage.

For example, when Se is simply vapor-deposited on a conventional Al plate or an AI vapor-deposited film at 45°C and normal humidity, it crystallizes and loses photoconductivity within just one week, whereas the method of the present invention If adopted, no substantial change will occur even after one month.

It was found that the improvement was particularly remarkable in the case of high humidity and high temperature.

Also. Although the adhesion between the photoconductive layer and the A1 film is not necessarily good, by adopting the method of the present invention, the overall adhesion is improved, and the printing plate can withstand the mechanical effects during copying.
It was also found that printing durability was improved.

Furthermore, it has been found that the electrical contact between the A1 layer and the photoconductive layer such as Se, that is, the mobility of charges during exposure, which is originally good, is further improved and the contrast is improved.

Examples are shown below for supplementary purposes.

Example 1 (including comparative examples) Biaxially stretched polyethylene terephthalate film (
1O-5T on top of (thickness 125 microns, width 100mm)
Aluminum (99.99% purity) under vacuum at orr
was vacuum deposited at a film speed of about 20 m/min using a resistance heating method using a boat with a thickness of 1.0 OOA.

The length of the boat is 100mm (in the width direction of the film)
and a width of 20 mm (in the direction of film travel).

Various types of Te were vacuum-deposited on this aluminum vapor-deposited layer in separate batches by resistance heating using the same boat.

Furthermore, the extremely thin layer of vapor deposition reduces the temperature of the boat and
The film speed is increased and the vacuum degree is 10-' respectively.
This was done with Torr.

Then, Se was vacuum-deposited to a thickness of 2,000 yen using a conventional method using resistance heating using a boat.

Immediately after the deposition, Se was found to be amorphous by X-ray diffraction and had good photoconductivity.

The results of these tests are shown in Table 1.

The adhesion of Se was determined from the peeling state when cellophane tape (manufactured by Chiban Co., Ltd.) was attached to the Se vapor-deposited film and subjected to heavy ringing in a 180° direction.

In addition, the charge mobility was determined by placing the Se-deposited film in a dark room with the aluminum-deposited layer grounded, corona-charging it, and then exposing it to light close to daylight color to determine the attenuation of the charged state. This was determined by looking at a cathode ray tube oscillograph.

Example 2 In Example 1, instead of depositing aluminum on a polyethylene terephthalate film, a sheet of aluminum foil with a thickness of 50 microns was laminated with an adhesive, and at the same time Te and Se were deposited. Ta.

The results showed almost the same tendency as in Table 1.

Note that the blank (without Te vapor deposition) was also not good.

Example 3 In Example 1, Te was vapor-deposited approximately 1001 m after AI was vapor-deposited using the apparatus shown in FIG.

The degree of vacuum is 10-'Torr (common), and when making an extremely thin film of Te, lower the boat temperature below the melting point of Te and reduce the amount of Te added (effective area for evaporation) to achieve the specified thickness. I made it so.

The film speed was the same <20 m/min.

The thickness of the deposited AI was the same <1,000, but the thickness of Te was varied.

The results of extracting samples with thicknesses close to those in Table 1 and comparing them were almost the same as those in Table 1, or even better, and the particularly good point was that the Se layer grayed out in high humidity. There was little discoloration such as blackening, and the adhesive strength and charge mobility were also better.

However, the blank and the thickness of Te, such as 500λ, are the first
The results showed the same unfavorable results as shown in the table.

Example 4 In Example 1, instead of vacuum deposition, Te was deposited by high frequency sputtering in a separate Pelger type sputtering device to a thickness of 0.5 mm and 5 mm.

Fifty people were evaluated and the results were almost the same as in Table 1.

Example 5 Biaxially stretched polyethylene phthalate film (thickness 125
After depositing nickel, tin, and palladium on the top of μ) by cathode sputtering to a thickness of 5 holes, each layer was vacuum-deposited with AI for 1,000 holes, and then Te was deposited to a thickness of 50 holes by vacuum evaporation before and after using the conventional method. Se is set to 1 by
,000 people.

As a result, the prevention of crystallization under high temperature and high humidity conditions was good.
In particular, the improvement effect at 5000 to 60°C was remarkable.

It was also found that the adhesive strength of Se and the overall adhesive strength were good and mechanically strong.

Furthermore, the charge mobility was also good. Example 6 In Example 1, Te was vapor-deposited on the aluminum film in accordance with the spirit of the present invention, and then, instead of Se alone, 5% and 10% of Te was added to Se.

20% and 30% were added at the same time to make a total of 2.0OOA.

The result is a blank, that is, S without Te pre-deposition treatment.
The products in which e and Te were simultaneously deposited exhibited anti-crystallization and anti-denaturation properties for 2 to 5 days, respectively, but experiments //62-6
The results corresponding to the results were approximately the same as those in Table 1 or slightly better than those shown in Table 1.

In addition, even in the part corresponding to /167, the average is 2 to 5 respectively.
The lifespan of degeneration was extended for several days.

[Brief explanation of drawings]

FIG. 1 shows an example of a continuous production apparatus for electrostatographic printing plates according to the present invention. FIG. 2 shows a cross-sectional diagram of an electrostatographic printing plate obtained according to the present invention. 1...Substrate, 2...A1 vapor deposition source, 3
...... Vapor deposited A1 layer, 4... Vacuum deposition source of Te, 5... Vacuum deposited Te layer, 6.
. . . Photoconductive layer containing Se or Te as a main component, 7 . . . Other photoconductive layer to be coated.

Claims (1)

[Claims] 1 Te is deposited on the aluminum film to a thickness of 05A to 300
An electrostatic copying printing plate made by vacuum-depositing an inorganic substance that exhibits photoconductivity in an amorphous state and mainly consisting of Se after a vacuum deposition process.