JPS62115447A - Developing process - Google Patents

Abstract

PURPOSE:To exactly reveal the gradation of a color balance shading by using a developer obtd. by contacting a silver halide color photographic sensitive material with a zeolite. CONSTITUTION:The zeolite 18 is packed in an absorbing tank 17. The developer is recycled from the developer tank 2 through a circulating pump 19 and a circulating pipe line 20. The zeolite is a crystalline aluminosilicate contg. an alkali and an alkaline earth metal. The amount of said zeolite is sufficient to use 0.1-1.0g per 1l of the developer. The zeolite is used by packing it into the absorbing tank as a pellet or a bead. Thus, the color photography having a less stain and a constant sensitivity, unitrast and color balance is obtd. If the stain concentration increases, and the photographic characteristic changes, the developer may recover to a good original state by using said absorber.

Description

DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL FIELD The present invention relates to a development processing method. The object of the present invention is to provide silver halide color photographic materials (films or
-) It is an object of the present invention to provide a technology for a developing processing method that can correctly express the color balance and brightness gradation of an object in the developing processing.

PRIOR ART AND THEIR PROBLEMS: Color images are generally formed in p-silver-genide color photographic light-sensitive materials by a process of applying a developer and a bleaching solution, washing with water, and drying. In the developer processing, the silver halide in the emulsion layer of the light-sensitive material is reduced by the color developing agent in the developer to precipitate silver, and at the same time oxidizes the color developing agent. The color developing agent oxidation products combine with couplers in the emulsion layers to form color images. In bleaching solution treatment, silver deposited in the emulsion layer is oxidized by an oxidizing agent such as EDTA/ferric complex salt in the bleaching solution, and then reacts with halide ions in the bleaching solution to form silver halide. Become. In the fixer treatment, the silver halide in the emulsion layer reacts with thiosulfate ions in the fixer and is dissolved and removed, leaving a color image in the emulsion layer. In the washing process, fixer components that have adhered to the photosensitive material are removed, and a color photograph is completed through a drying process.

In recent years, a bleach-fix solution made by combining the above-mentioned bleach solution and fix solution has been used for developing 1cce of silver halide color paper and the like. In this case, a color image is formed from the silver halide color photographic light-sensitive material by a development process of developer solution, bleach-fix solution, washing with water, and drying.

To develop a large amount of silver halide color photographic light-sensitive materials, each processing tank of the developing machine is first filled with each processing solution called a tank solution, and then each processing solution called a replenisher is added to each tank at the same time as processing the light-sensitive material. It is common to supply and overflow the treatment tank. Although the compositions of the tank liquid and the replenisher are generally different, the composition and supply amount of the replenisher are determined so that the composition of the tank liquid does not change during processing of the photosensitive material.

When color photographic materials are processed by the above-mentioned development processing method, the color balance and gradation of brightness and darkness of the subject often change over time. for example,
When color paper is developed using the processing process of developing solution - bleach-fix solution - washing and drying, the magenta density (linear optical density) and stain of the color vapor will change after a few days compared to the case of using a new tank solution. Phenomena that are not interesting in terms of photographic characteristics often occur, such as abnormally high density.

Structure and Effects of the Invention The present inventor has arrived at the present invention as a result of intensive research into measures to prevent such phenomena.

Ru. That is, the present invention is a development processing method comprising processing a silver halide color photographic light-sensitive material using a developer brought into contact with zeolite.

The method of the present invention will be explained with reference to FIG. 1, taking color vapor development treatment as an example. In Figure 1, the developing machine! is the developer tank 2. Bleach-fix tank 3. It consists of a washing tank 4 and a drying room 5.

The color paper 6 is connected to a loop-shaped drive belt 7 and driven, and the color paper 6 is driven into a developer tank 2. Bleach-fix tank 3
．． Washing tank 4. It passes through a drying chamber 5 and becomes a color photograph 8. 9 is a motor that moves the drive belt 7, and 10 is a roller. The developer tank 2 contains a replenishing developer 11.
is replenished and overflows from 12. The bleach-fix solution tank 3 is replenished with a replenishing bleach-fix solution 13 and overflows from the bleach-fix solution tank 14.

Water 15 is supplied to the water washing tank 4 and overflows from the water 16. 17 is an adsorption tank.

The adsorption tank 17 is filled with zeolite) 18, and the developer is supplied from the developer tank 2 to the circulation pump 19 and the circulation vibe line 2.
(It is circulated from JK. Stainless steel or polyvinyl chloride is used as the material for the adsorption tank and piping.

The developer of the present invention refers to a color developer for silver halide color photographic light-sensitive materials. Color developing solutions generally consist of a color developing agent, a preservative, an accelerator, and an inhibitor. A color developing agent is a chemical that has the property of reducing the latent image of silver halide in the emulsion layer of a color light-sensitive material, and at the same time, its oxidation product reacts with the coupler in the emulsion layer to form an image. Phenylenediamine sulfate, hydroxyethyl/ethyl Yubara 7 Enylenecyamine Qam+2-
Amino-5-diethylaminotoluene hydrochloride 14-amino-N-ethyl-N-(β-methanesulfonamidoethyl) -m -) luidine monosulfate l hydrate and 4
-amino-N-hydroxyethyl-N-ethyl-m-)
Compounds of the N,N-difurkyl-P-7 22-diamine type such as luidine sulfate are used. The preservative is a chemical added to prevent the color developing agent from being oxidized in the air, and sodium sulfite, potassium sulfite, hydroxylamine sulfate, etc. are used. Accelerators are chemicals that strengthen the reducing action of color developing agents, and include alkali salts such as sodium hydroxide and potassium hydroxide; alkaline salts such as sodium carbonate, potassium carbonate, tribasic sodium phosphate, and borax. Ru. Inhibitors are chemicals such as sodium bromide and potassium bromide that strongly inhibit the development of underexposed areas of silver halide photosensitive materials and remove fog.

Potassium iodide etc. are used. Benzyl alcohol or sodium thiocyanate may be added to the background color developing solution for the purpose of helping the color developing agent penetrate into the emulsion layer of the light-sensitive material. In addition, an anti-settling agent such as sodium hexametaphosphate or EDTA 2Nm salt may be added to the color developing solution.

The zeolites of the present invention are crystalline fluminosilicates containing alkali and alkaline earth metals. Its chemical composition is M, /n0-All, O, -XS iO, -YH
, O. M: Alkali or alkaline earth metal n: Valence of alkali or alkaline earth metal (8i
-0-8i or 8i-0-All), and the number of oxygen atoms becomes the size of the pore which defines the size of the cavity. Zeolites include natural zeolites and synthetic zeolites, and the present invention may use either zeolite.

When zeolites are classified according to their skeleton structure, they are classified as Single 4-ring (Analcime).
s Single 6-ring (offvetite
)s Double 4 ring (A type) Dou
ble 6-ring (X type IY type) g Com
plex 4-1 (Edingtonite), C
complex 5-1 (Mordenite) Comp
lex 4-4-1 (C1inoptilolite
) However, in the present invention, zeolite having any skeleton may be used. Y-type zeolite and mordenite (M
The effect on photographic properties was particularly pronounced.

The amount of zeolite used in the present invention varies depending on the type of zeolite and developer, but it is from 0.1 to 1 liter of developer.
1.01 is sufficient. The zeolite of the present invention is preferably used in the form of pellets or beads and packed in an adsorption tower as shown in FIG.

If zeolite in the form of pellets or beads is packed in a non-woven fabric bag and then filled into the suction bag 41, it is easy to take it in and out from the suction bag.

According to the method of the present invention, it is possible to always obtain color photographs with a constant sensitivity, second last, color bar, and lance with little stain. Even if the stain density increases or the photographic properties change, the use of the adsorbent of the present invention can restore the original good state.

The reason why the method of the present invention improves photographic properties is not clear, but the reason is that, for example, the zeolite adsorbs and removes fixer components such as ammonium ions that are attached to loop-shaped K and brought into the developer. It is thought that this is the case.

The method of the present invention will be explained in detail below with reference to Examples. It is clear that the method of the invention is not limited in this way.

Examples Table 1: A developer (tank solution) and a bleach-fix solution (tank solution) having the compositions shown in Table 1 were prepared in the developer tank 2 of the developing machine 1 shown in FIG.
and bleach-fix solution were filled in tank 3, respectively, and the silver halide color paper was developed. Currently, in processing, the developer shown in Table 1 A is used in proportion to the throughput of color paper (
A bleach-fix solution (replenisher) and a bleach-fix solution (replenisher) were supplied to each tank, and the composition of the tank solution was always kept constant. The development processing conditions are shown in Table 2.

In order to develop the photographic characteristics of color paper, control paper manufactured by Fuji Photo Film Co., Ltd. is developed once a day, and the stain area (lowest exposure area), low optical density area (LD), and high optical density area (HD) are developed. ) and contrast) () ID-LD)
were measured in red, green, and blue optical densities, respectively. The results are shown in Table 3.

After 58 days of processing with the new developer and new bleach-fix solution (both tank solutions), the blue optical density of the stain area and the green optical density of the low optical density area, high optical density area, and wet last area increased abnormally. . This trend remained the same after 30 days. Adsorption mechanism K directly connected to the developer tank of the 30-day extraction/detachment machine
It was filled with Y-type zeolite and a developer was circulated (see Figure 1). Yfi zeolite is U, 30 per liter of replenishing developer.
, V every day.

After 35 days of removal, the blue optical density of the dye area, the low optical density area, the high optical density area, and the green optical density of the contrast areas were restored to normal. This trend continued for a long time thereafter.

Table 1 @2 Table

[Brief explanation of drawings]

Figure 1 shows three color papers (photosensitive materials) of the present invention.
It is a schematic diagram of the apparatus which processes 3Ls. In the drawing, l
is the developing machine, and 2 is the developer tank. 3 is a bleach-fix tank, 4 is a washing tank, 5 is a drying room,
6 is a color paper, and 8 is a color photograph 7 is a drive belt for conveying the color paper.

Claims (1)

[Claims] A development processing method comprising processing a silver halide color photographic light-sensitive material using a developer brought into contact with zeolite.