JPS5952418B2 - Processing method for color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the following general formula / , \noz/ (wherein A is a residue obtained by removing one hydrogen atom from an active methylene group of a yellow image forming color former having an active methylene group) Z is
The atomic group directly bonded to N among the atomic groups necessary to form a heterocycle is -Co- and -500-.

However, when the atomic group directly connected to N is -Co-, Z
The atoms forming the nitrogen-containing heteromonocyclic nucleus together with -N<C0- in the above general formula are not composed only of carbon atoms. This invention relates to a processing method for processing a silver halide color photographic light-sensitive material containing a yellow color forming agent shown in ), and its object is to obtain a completely yellow image when processed in a bleach-fixing bath.

Conventionally, color photographic materials are processed through the processing steps of development -> fixing -> bleaching -> fixing -> stabilization, but in order to shorten the processing time, there is a method that involves the processing steps of development -> bleach-fixing -> stabilization. This is because bleaching and fixing are carried out at the same time, which greatly shortens the processing time, making it extremely advantageous for rapid processing as has been the case in recent years. However, this method has various drawbacks.

That is, the oxidizing agent used in the bleach-fixing bath is one with weak oxidizing power, such as ethylenediaminetetraacetate iron salt (EDTAFe monosalt), which has a bleaching edge compared to oxidizing agents such as red blood salt. Very weak.

For this reason, not only is the bleaching of iron delayed, but some color formers contained in photosensitive materials do not develop color sufficiently through development alone, and are brought into the bleaching bath in their leuco form, where they are bleached for the first time. The color is perfect. In this case, if the bleaching blade is weak, the color development will be insufficient. That is, when rapid processing is performed using a bleach-fix bath, the oxidation-reduction potential of the bleach-fix bath is weak, so the color development of the coloring agent is incomplete, and... The developed silver is not sufficiently bleached, resulting in color turbidity, which is a serious drawback. Furthermore, when processing with a bleach-fixing bath immediately after processing with an alkaline color developing bath, color staining is more conspicuous than when a stop bath is provided between the two baths. .

The causes of this color staining include the following matters. That is, the color developing agent in the color developing bath remains in the color photographic light-sensitive material as it is even after development processing, and since there is no stop bath, it is subjected to the bleach-fixing 2 processing in that state, resulting in excess color development being brought in. The main drug reacts with the yellow coloring agent, resulting in color staining. Similarly, the benzyl alcohol in the color developing bath is brought into the bleach-fixing bath while remaining in the light-sensitive material, where the benzyl alcohol! It is oxidized to benzaldehyde, and the generated benzaldehyde reacts with the yellow coloring agent to cause color staining. The present invention provides a processing method in which the color forming agent sufficiently develops color and does not cause color turbidity even when processed in a bleach-fixing bath as described above.

Another object of the present invention is to provide a processing method that does not cause color staining even when bleach-fixing is performed immediately after processing with an alkaline color developing agent.

The color photographic light-sensitive material used in the present invention has the following four general formulas (where A is a residue obtained by removing one hydrogen atom from the active methylene group of a yellow image forming color former having an active methylene group, Z is a hetero The atomic groups directly bonded to N that are necessary to form a ring are -CO- and -SO2-.

However, when the atomic group directly connected to N is -CO-, Z
The atoms forming the nitrogen-containing heteromonocyclic nucleus together with -Nku00- in the above general formula are not composed only of carbon atoms. ) Representative specific examples of silver halide color photographic materials containing a yellow color forming agent represented by the above general formula include the following.

X. Y is hydrogen, alkyl, acyl, substituted or unsubstituted aryl group, aralkyl group, Z is hydrogen, alkyl, substituted or unsubstituted aryl group, aralkyl group) (in the formula R1, R
2 is hydrogen, alkyl, substituted or unsubstituted aryl, aralkyl, cycloalkyl, benzylidene, carboxyl group) (where x is hydrogen, acyl group, alkyl group, carboxylmethyl group, alkoxycarbonylmethyl group, carbamylmethyl group, Substituted or unsubstituted aryl group, aralkyl group, nitro group, amino group.

Y. Z is hydrogen, alkyl group, ureido group, substituted or unsubstituted aryl group, aralkyl group, benzylidene group, styryl group, aniline group) (in the formula, R1 and R2 are lower alkyl groups x is hydrogen, halogen, alkoxy Y is hydrogen , halogen, amino, acylamide, ureido, lower alkyl, alkoxyl, hydroxyl, and the Keiko group necessary to form a benzene ring with x) (in the formula R,
R.

is hydrogen, alkyl, substituted or unsubstituted aryl, or aralkyl) When color photographic materials containing the above-mentioned yellow color formers are processed in a bleach-fixing bath with a low redox potential, they have a good desilvering effect and the dye The color development of the image is also perfect.

In addition, the coupling speed is fast and the color development efficiency is high. Also,
Even if such a color photographic light-sensitive material is subjected to color development processing without intervening a stop bath, color staining will not occur even if it is immediately subjected to bleach-fixing processing. When producing such color photographic materials, the coloring agent may be a high boiling point solvent such as dibutyl phthalate or tricresyl phosphate, ethyl acetate,
It may be added by dissolving or dispersing it in a low boiling point solvent such as butyl acetate.

Next, after exposing the photosensitive material as described above, it is developed, and the developing agent used is diethyl-P-phenylenediamine hydrochloride monomethyl-P-phenylenediamine hydrochloride dimethyl-P-phenylenediamine hydrochloride. Salt 2-amino-5-diethylaminotoluene hydrochloride N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-Aminoaniline sulfate and the like can be effectively used.

After development, bleach-fixing is performed without washing with water, and examples of the oxidizing agent include.

After the bleach-fixing process, the image is washed with water and then subjected to a stabilization process, and a typical stabilizing bath is one that lowers the pH to around 4 and increases the stability of the image during storage.

The present invention will be described below with reference to Examples. Example 1 As a yellow coloring agent, 4.1 g of the compound of the following formula was mixed with 4.1 ml of dibutyl phthalate. It was dissolved in 12.3 ml of ethyl acetate, and 20 ml of a 5% aqueous solution of Alkanol B (a surfactant manufactured by DuPont) and 40 ml of a 10% gelatin solution were added for protection dispersion.

This dispersion was mixed with a fine-grain silver chloroiodobromide emulsion prepared from 60 g of silver nitrate.
Sample (1) was obtained by coating on baryta paper (containing 0g/1 mole of silver halide) and drying.

On the other hand, as a yellow color former, yellow color former 4 used in the present invention
．． Sample (2) was prepared in the same manner as the above sample (1) using 2 g.
) was created.

Samples (1) and (2) obtained above were exposed to light through a light wedge, and then sequentially treated with the following treatment baths.

Table 1 shows the reflection density of the sample after drying, which was measured using a densitometer through blue and red filters.

Note that, as is clear from the red density table-1 at a location where the blue density is 1.0, the red density of sample 2 (invention) is significantly lower than that of sample 1 (conventional).
Excellent color saturation.

Example 2 Samples containing equal moles of each of the following yellow color formers were prepared in the same manner as Sample 1 of Example 1, and these samples were treated in the same manner as in Example 1 to produce blue and Table 2 shows the results of measuring the red color density.

[Coloring agent]

In the sample of the present invention (234), the blue density is extremely low, while the red density is sufficiently low as in the sample of Example 1, and the desilvering effect of developed silver is excellent.

Example 3 A paper surface coated with a polyethylene layer is used as a support, and the following layers are sequentially coated thereon.

Two types of samples were prepared, differing only in the yellow color forming agent. (1) Blue-sensitive silver chloroiodobromide emulsion (AgIl mol%
Emulsion (sample 1) containing AgBrSO mol%, gelatin 250g/halogen (contains 1 mole of silver) and containing the following yellow coloring agent (2) Gelatin intermediate layer (3) Edge-sensitive salt odor containing the following magenta coloring agent Silver emulsion (containing AgBr5O mol%, gelatin 250g/silver halogen 1 mol) (4) Gelatin intermediate layer (5) Red-sensitive silver bromide emulsion (AgBr5O mol% containing, gelatin 250g/halogen) containing the following cyan coloring agent (contains 1 mole of silver) (6) Sample 1 is a photosensitive material layered with a gelatin protective layer, and the following yellow color former is used in place of the above yellow color former, and Sample 2 is prepared in the same manner as above.
It was created.

After exposing Samples 1 and 2 obtained above through blue, green, and red gelatin filters and a light wedge, the same treatment as in Example 1 was performed, and the reflection density of the colored portions of the treated samples was determined to be blue. , green, and red filters, and the relative values of each concentration were determined, and the results shown in Table 3 were obtained.

As is clear from Table 3, the yellow coloring dye of Sample 2 according to the present invention has a lower green and red density relative to the blue density than Sample 1, and has less color turbidity.

Claims (1)

[Claims] 1 The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ , Z is an atomic group necessary to form a heterocycle, and the atomic group directly connected to N is -CO-, -SO_2-. However, when the atomic group directly connected to N is -CO-, Z
In the above general formula, there are ▲numerical formulas, chemical formulas, tables, etc.▼, and the atoms forming the nitrogen-containing heteromonocyclic nucleus are not composed only of carbon atoms. ) After processing a silver halide color photographic light-sensitive material containing a yellow color forming agent shown in (a) with an alkaline color developing solution containing a para-phenylene diamine color developing agent, a bleach-fixing solution containing a silver halide solvent and a silver oxidizing agent is immediately applied. A method of processing color photographic materials in which the silver compounds produced are removed (stabilized) by washing with water.