JPS5931057B2 - Reinforcement toning liquid for photosensitive aluminum plate - Google Patents

Description

Detailed Description of the Invention The present invention uses an anodized aluminum plate as a support,
The invention relates to an intensifying toning solution for a photosensitive aluminum plate containing silver halide as a photosensitive substance in the pores of the anodic oxide film on the surface of the support. This relates to the intensifying toning liquid used.

The greatest feature of silver salt photosensitive materials that use anodized aluminum plates as supports is the corrosion-resistant and durable coating of aluminum oxide (hereinafter referred to as alumite) layer formed on the surface of the aluminum plate by anodization. protect silver images,
The purpose is to obtain recorded images with good durability.

It is known from many studies on alumite that the alumite layer has pores (or pores) that can be filled with photosensitive silver salt, and this is reported in the Journal of the Electrochemical Society (J, Elec, Ch.
The structure is clearly explained in Em, Soc, ) 10O, (9), 411.

Alumite coatings are made up of cells, hexagonal pillar units that stand perpendicular to the metal surface.
Pores of 100-1000A are present. Silver salt photosensitive materials using anodized aluminum plates are well known from the specifications of U.S. Pat. No. 2,115,339, U.S. Pat. An essential condition for obtaining durable images is that the silver halide is not simply placed on the alumite layer, but is filled into the pores of the alumite layer.

A durable silver image on a photosensitive aluminum plate is formed through the following processing steps.

Exposure → development/fixing → reinforcing force → sealing force, and sealing is the key to forming a recorded image with good durability.

The sealing seals the formed silver image into the alumite layer, shielding it from the outside atmosphere and protecting it. Various sealing methods and sealants are known, but they do not require special equipment, the image forming substance is silver, and they are often partially colored with alumite dye or used in combination with dye. Boiling pore sealing method,
Nickel salt sealing fluids are commonly used. Sealing fluids containing strong oxidizing agents, such as dichromate sealing fluids, cannot be used as they will damage the silver image. In the boiling sealing method, sealing is usually performed for 10 minutes to 1 hour.

If a silver image that has only been developed and fixed is boiled and sealed, it will turn brown and fade. Traditionally, as a method to prevent discoloration and fading during sealing, so-called gold toning solutions made of water-soluble gold compounds such as thiocyanate and chloroauric acid, and so-called tin supplements made of a combination of ferricyanide salts and stannous salts have been used. It is known to immerse a silver image after development and fixation with a liquid.

Two things are expected from the reinforcing process of photosensitive aluminum plates. One is to prevent browning due to the heating during sealing, and the other is toning the silver image tone to pure black due to the size of the image-forming silver. It has been found that the intensification toning liquid of the present invention has both of the above-mentioned effects, and can reduce the required processing time to about 1/4 in the intensification process, taking into consideration the light resistance and durability of the finished product. .

The intensifying toning liquid of the present invention has a water-soluble gold compound of 10-4 to 1
0-1 mol/l, preferably 1[2 to 10-1 mol/l, and contains sulfite of 10-57 mol/l or more,
Furthermore, the molar ratio of water-soluble gold compound and sulfite is 1:1 to 10.
It is characterized by a ratio of 0:1.

There are no particular restrictions on the processing conditions, but preferably the temperature is 15-25
℃, and the treatment time is 20-30 seconds.

Examples of the water-soluble gold compound include gold salts, complexes, oxygen acids, salts of oxygen acids, complex acids, and salts of complex acids, and any water-soluble gold compound may be used.

For example, gold halides such as gold trichloride, gold (1) chloride (111 gold tribromide), lithium salts, sodium salts, potassium salts, ammonium salts of chloroauric acid, bromic auric acid, and tetrachloroauric acid salts, gold halide complex acids such as sodium salts, potassium salts, rubidium salts, and ammonium salts of tetrabromo gold (auto) acid, and their salts, diammine gold (1) chloride, diammine gold (1) bromide, tetrabromo gold (auto) acid tripercrotate, tetraamine gold (11)
Examples include gold ammine complexes such as trinitrate, tris(tetraammine gold) perchlorate, and tetrasulfate, and trisodium dithiosulfate gold(1) acid. Among these, chloroauric acid is particularly preferred.
Examples of sulfites include alkali metal salts such as sodium and potassium, ammonium salts, and sodium hydrogen sulfite.

Hereinafter, it will be explained in more detail with reference to Examples.

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

After washing with water and drying, the following silver nitrate solution was applied and dried. A silver nitrate solution and then the next halogen solution were applied and dried.

The halogen solution was further coated with the following halogen solution, washed with running water for 10 seconds, and then dried.

A negative was adhered to the obtained photosensitive silver salt aluminum plate under reduced pressure and exposed to light at 1 m for 40 seconds using a 100 watt photographic light bulb.

The image was developed and fixed using a roller processing machine using a quick developer (from Example 1 of British Patent No. 1287179) and a quick fixer (from Example 1 of Japanese Patent Publication No. 48-28296). After washing with water for 30 seconds, it was immersed in the solution for 30 seconds.

After washing with water for 30 seconds The pores were sealed for 20 minutes with a pore sealing solution.

The color tone of the finished silver image was pure black, and the blackening density of the image was also sufficiently high. The comparison with when using gold toning liquid is shown in the first part below.
Shown in the table. As a method of displaying the color tones in the above table, the reflection spectral ratios of 400 mμ and 700 mμ at an image density with a reflectance of 550 mμ of 15.9% were measured using a spectrophotometer and compared.

Since it is expressed as 700/400, the larger the value, the better the temperature is controlled, and the ratio indicating pure black is approximately 1.1 to 400.
At 1.3, when the intensified toning method of the present invention was used, the silver image had a slightly purplish-black tone, although it was not the conventional gold toning method.

In addition, the reinforcing time was determined by considering both the effect of preventing discoloration and fading during sealing and the weather resistance of the image.

The light resistance test was carried out using the Sash Yarn Weather Meter.
00 hours (according to the JISDO2O5 commentary, 150 hours is equivalent to one year of outdoor exposure.

), and the conditions under which the image density could be maintained at 1.1 or higher were defined as the intensification time. As is clear from the above table, the intensification toning liquid of the present invention is comparable in performance to the conventional intensification liquid, and the intensification time can be reduced to about 1/4.

Example 2 The developed and fixed silver image on the photosensitive aluminum plate shown in Example 1 was treated with an intensifying toning solution for 10 to 15 seconds and sealed by boiling in deionized water for 30 minutes.

Similar to Example 1, reinforcing effect, discoloration/fading prevention effect, and weather resistance were obtained. Example 3 The developed and fixed silver image on a photosensitive aluminum plate was boiled and sealed for 20 minutes with an intensified toning solution for 10 to 20 seconds with an intensified toning solution.

Claims (1)

[Claims] 1 Contains 10^-^4 to 10^-^1 mol/l of a water-soluble gold compound, 10^-^1 mol/l or more of a sulfite, and has a molar ratio of water-soluble gold compound:sulfite of 1: 1-100
; Intensifying toning liquid for photosensitive aluminum plate, which is No. 1.