JPS5832700B2 - Kankousei Aluminum Bannoseizohouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photosensitive aluminum plate with improved storage stability. , relates to a method of coexisting a divalent copper salt in an alkali halide solution when forming silver halide.

Conventionally, regarding silver salt photosensitive materials using anodized aluminum plates, U.S. Pat. No. 2, 15.339,
It is described in the specifications of the same No. 2,126,017 and the same No. 2,766,119, etc., and is used for name plates, scale plates, decorative plates, circuit diagrams, wiring diagrams, etc.

Many studies have been reported on the aluminum oxide film (hereinafter referred to as alumite) formed on the aluminum surface by anodization, and it has been published in the Journal of Zui Electrochemical Society.
l of the Electrochemical
5ociety), Vol. 100, No. 9, pp. 411-419 (1953), the structure is clearly explained.

According to this, an alumite film is made up of "cells," which are hexagonal pillar structural units that stand perpendicular to the metal surface.
In the center of this cell there are usually 100-100 OA pores.

The most important feature of silver salt photosensitive materials that use anodized aluminum plates as supports is that the corrosion resistance of the alumite film protects silver images and creates semi-permanent recorded images.

Therefore, it is necessary to fill the pores of the alumite with the photosensitive pseudosalt instead of placing it on the alumite film.

Silver halide used for ordinary photographic light-sensitive materials is aged by reacting silver nitrate with alkali halide in a gelatin solution and maintaining it at a constant temperature.
~1. Particle sizes in the O micron range are obtained.

On the other hand, the photosensitive silver salt that can be filled into the pores of alumite is limited to a grain size of 1000A (0.1 micron) or less, so it is impossible to use silver halide for ordinary photographic materials. It is.

For this reason, the photosensitive silver salt of the photosensitive aluminum plate is prepared by filling the alumite pores by sequentially applying or impregnating a silver nitrate solution and an alkali halide solution, as also disclosed in the patent specifications listed above. are doing.

The photosensitive silver salt filled in the pores is susceptible to fogging due to the influence of surrounding aluminum and residual ions of the anodic oxidation solution in the alumite layer, shortening the shelf life of the photosensitive aluminum plate.

As a preventive measure against this, the method of using a polymeric binder and the method of adding dichromate or red blood salt to a silver nitrate solution or an alkali halide solution are described in the above patent specification, and the method is described in the above patent specification. A product with an effective shelf life of ~6 months has been obtained.

However, for reasons of sales and use, such a period of time is not sufficient at all, and from the standpoint of environmental conservation, the use of the above salts poses difficult problems in the treatment and treatment of waste liquid, etc. ing.

Therefore, an object of the present invention is to provide a method for manufacturing a photosensitive aluminum plate with excellent storage stability.

As a result of various studies, the present inventors have found that this purpose is achieved by coexisting a divalent copper salt in an alkali halide solution when forming a photosensitive silver salt in the pores of an aluminum oxide film. This was achieved by extending the shelf life to 1 to 2 years.

The photosensitive aluminum plate of the present invention contains a divalent copper salt in the pores of an aluminum oxide film formed on the surface of aluminum when silver halide is formed from a hydrophilic silver nitrate colloid and an alkali halide solution. Obtained by coexisting.

In the above components, the aluminum may be substantially pure aluminum or an aluminum alloy containing various metals such as copper, iron, silicon, zinc, and manganese.

Examples of the hydrophilic colloid include gelatin, polyvinyl alcohol, methyl cellulose, gum arabic, and agar, with gelatin being particularly preferred.

As the photosensitive silver salt, mixed silver halides such as silver chloride, silver bromide, silver chlorobromide, etc., which are formed by coexisting a divalent copper salt in silver nitrate and an alkali halide solution, are suitable, and in particular, Silver chloride and silver bromide are preferred.

As the divalent copper salt added to and allowed to coexist in the halogenated alkali solution during silver salt formation, cupric nitrate, cupric chloride, cupric bromide, cupric acetate, and the like are preferable.

These copper salts have a concentration of 0 per 11 in an alkali halide solution.
．． A photosensitive silver salt can be formed by adding and coexisting an amount ranging from 0.02N to a saturation amount, preferably 0.03N or more.

The photosensitive aluminum plate of the present invention has high sensitivity, no fogging, and has excellent long-term storage stability, but it is unclear why such an effect is achieved when a divalent copper salt is added.

Further, the photosensitive aluminum plate obtained by coexisting the divalent copper salt of the present invention can be subjected to subsequent development, fixing, etc. in the same way as conventional photosensitive aluminum plates.

The present invention will be explained in more detail below with reference to Examples.

Example 1 A corrosion-resistant aluminum alloy plate containing 0.15% copper was heated for 30 minutes in an electrolytic solution containing 5% oxalic acid and 3% potassium oxalate.
Electrolysis was performed by passing a direct current of 2 A/di at 60° C. for minutes.

Thereafter, the aluminum alloy plate was washed with water and dried, and then a silver nitrate solution having the following composition was applied and dried.

Silver nitrate 300g Gelatin 5g Concentrated nitric acid 1cc Distilled water 11 Subsequently, an alkali halide solution having the following composition was applied and dried.

Potassium bromide 50g Cupric nitrate log 0g distilled water ll Furthermore, a solution having the following composition was applied, washed with water for 30 seconds, and then dried.

Potassium bromide 5 (Bi' distilled water
IA The photosensitive aluminum plate thus obtained could be used without any fogging even after being stored for more than one year.

Example 2 A silver nitrate solution having the following composition was applied to an aluminum plate electrolyzed by the method described in Example 1 and dried.

Silver nitrate 50g Polyvinyl alcohol 5g Distilled water ix Subsequently, an alkali halide solution having the following composition was applied and dried.

Sodium chloride 50& Cupric chloride 2g Distilled water ll Further, the following solution was applied, washed with water for 10 seconds, and then dried.

Sodium chloride 30g Potassium bromide 3g Distilled water ll The photosensitive aluminum plate thus obtained is 1 to 2
Even after storage for a year, no fogging occurred, and other photographic properties did not deteriorate, so it could be used without any problems.

Claims (1)

[Claims] 1. In producing a photosensitive aluminum plate containing silver halide in the pores of an anodized aluminum film,
A method for producing a photosensitive aluminum plate with improved storage stability, characterized in that a divalent copper salt of 0.02 N or more per liter is allowed to coexist in an alkali halide solution when forming silver halide.