JPS5818630A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an image of superior quality stabilized for a long term, by processing a silver halide color photosensitive material subjected to fixing or bleach-fixing, and stabilization processing, with a solution containing an oxidizing agent, and drying it. CONSTITUTION:A silver halide color photosensitive material is processed with a fixing or bleach-fixing solution containing thiosulfate, and then treated with a stabilization processing solution containing a buffer agent, a chelating agent, a surfactant, a sulfur compound, an onium salt, a hardening agent. Then, it is treated with a processing solution containing 0.01-100g/l oxidizing agent, such as peroxodisulfuric acid, and when needed, a buffer agent, a chelating agent, a fluorescent whitening agent, etc., and dried, thus permitting deterioration of photographic characteristics due to intrusion of thiosulfate into a color developing bath in an automatic developing machine to be prevented, and a dye converted into a colorless leuco type by the stabilization processing to be restored to the initial color.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to the Hague silver oxide color photographic light-sensitive material method, and more specifically, when the water washing step is omitted, the material is processed with a processing solution containing a 41 oxidizing agent. Jintoyo p1
A stone related to the processing method of 4-silver-genide photographic light-sensitive materials that can form images of stable and excellent quality even during long-term storage.

-Kinni Kak-Photography III Several colors are developed with a color developer, then bleached, fixed,
Washing with water and stabilizing treatment make formation of the film more difficult.

Conventionally, in order to speed up the process, a bleach-fixing process has been used in which a Kll white process and a fixing process are performed simultaneously.

In such a bleach-fixing process 11, thiosulfate is generally used as a fixing agent for removing round steel and unexposed halogenated steel that have been bleached with bleaching powder.

There are thiocyanates, halides, thioethers, acetates, etc. as fixing agents that can replace thiosulfates.
In both cases, the solubility of silver ions in dilute solutions is poor, and the desilvering action of removing unexposed halogens and silveride is difficult.
Nine thiocyanate produces more cyanide ions than light, so it is not widely used as a fixing agent.

In addition, in recent years, with the use of photofinishers that automatically and continuously process photographs, issues of conservation of the ancient burial mound and water resources have become important), and fixing baths or bleach-fixing baths have been used. string
In the washing process, the amount of O washing water used has been reduced, and as a more fundamental solution, there is a strong desire for an easy method of regenerating the washing water or for eliminating the washing process.

Ion exchange resin methods and reverse osmosis methods are used as methods for regenerating washing water. Although these methods are technically possible to protect, they have the disadvantages of high initial cost, large installation area, and complicated operation, making them unusable. A method of performing 1lt- is proposed in IEI No. 55-83067@device.

However, it has been found that the method of performing stabilization treatment without this water washing step has the following drawbacks.

That is, using a belt conveyance type automatic developing machine, at 9 o'clock,
This is due to the fixing solution or bleach-fixing solution being mixed into the stabilizing bath, and also due to thiosulfate being taken out from the stabilizing bath by adhering to the belt and being carried back into the color developing solution. It has been found that there are drawbacks such as increased contrast in photographic characteristics and chromatinization of cyan dyes.

In other words, this drawback is that in stabilization plants where the washing step after fixing or bleach-fixing is omitted, the thiosulfate contained in the fixing bath or bleach-fixing bath is removed during continuous processing. Particularly when using an automatic processor, the leader belt, leader/film hanger, hanger peg, etc. that is used repeatedly to support and transport the photosensitive material. This is an inconvenience that arises from the fact that thiosulfate adheres to the dye and reverses Ks from the stabilizing bath into the color developing solution.

A tenth object of the present invention is to provide a method for processing a photosensitive material that prevents abnormalities in photographic properties due to the contamination of thiosulfate into a color developing bath in an automatic processor. A second object of the present invention is to provide a method for processing a sensitive material by restoring the color of the dye that has been leuco-converted by the stable habitat 11.

According to the above-mentioned invention, the fixing material containing thiosulfate is treated with a bleach-fixing solution, and is processed at a stabilization processing factory without going through a washing process. In the method, this is achieved by performing a treatment with a treatment solution containing an oxidizing agent between the stabilization treatment step and the drying step.

In the present invention, KI between the line stabilization treatment process and the 11LtIA engineering duck
In a place containing an N-oxidizing agent, W* is brought into contact with a photosensitive material and a carrier substance carrying a photosensitive material O, thereby reducing the temperature at high temperatures in a p% drying factory IIi.
, by decomposing large thiosulfate that adheres to the carrying material of the photosensitive material during drying (at 50°C or higher) and rendering it harmless. At the same time, cyanide produced in a stable habitat ia* with low - during the drying process @ This is achieved by oxidizing the leuco form of the pigment and returning it to a pigment.

Oxidizing agents that are effectively used in this invention include permanganic acid (salt), chromic acid (salt), 1M11 (salt), halogens such as chlorine, hydrogen peroxide, etc., or water peroxide. peroxides, peroxo disulfuric acid, peroxosulfuric acid, peroxophosphoric acid, peroxocarbonic acid, peroxoboric acid, etc. Acid Misaki O oxygen acid (salt)
, ozone, etc., but preferable compounds such as peroxide, peroxosun (salt), oxygen acid (salt), ozone, etc. give good results because they release hydrogenated oxygen. Mention may be made of hydrogen peroxide, percarbonates, perborates and persulfates. However, the oxidized rigid wire used in this method is not limited to the above.As a method for incorporating the compound of the present invention into the treatment solution, electrolysis or the like is used to generate an oxidizing agent in the solution. It's okay.

The amount of the oxidizing agent added in the present invention is α01 to
It is preferable to use it in the range of 100f, more preferably α1 to 8Of. Even in small amounts, the effect of the present invention is not sufficient.

10 (or even 17A) in large amounts may deteriorate the stability of the color developer.

In addition, other additives may be added to the treatment solution containing the oxidizing agent used in Hontei@, such as borates, metaborates, borax, phosphates, monocarboxylate salts, etc. as buffering agents. Dicarboxylate, polycarbonate, sulfate, hydroxide, potassium hydroxide, etc. can be added. 77 nopolycarboxylic acid salt as a chelating agent in a bottle
Novoliphosphonic acid, phosphonocarboxylic acid, alkylidene diphosphonic acid, polyphosphoric acid, birophosphoric acid, metaphosphoric acid,
Gluconate and the like can also be added.

Other compounds that do not react with oxidizing agents or have low reactivity include fluorescent brighteners, surfactants, antifungal agents, antistatic agents, etc., which are known as stabilizing bath additives. It becomes cloudy due to addition.

In particular, the supporting material for the photosensitive material is a round device that supports the photosensitive material, and #i in the case of manual development.
, reels etc. are used, but the present invention makes FiIf! I
K: This is a method that is processed in large quantities in an automatic stacking machine, and includes (a) a conveying leader, a leader belt, an endless belt, a film hanger or a film hanging hanger, and a holder for the hanger.

Method of bringing the oxidizing agent-containing solution of the present invention into contact with the sensitive material The sensitive material may be immersed in K11l in the same way as the general solution 11m, but the oxidizing agent in If it does not react, it may be applied to the emulsion side of the photosensitive material, both sides of the conveyance leader, and the conveyor belt, or it may be sprayed on.

Furthermore, a processing liquid containing the oxidizing agent of the present invention and a sensitive material OI
I. Opening time at contact The time required for the purpose of incorporating the oxidizing agent into the sensitive material and adhering the Kll-forming agent to the conveyor belt etc. may be a short time, preferably within 2 minutes.

The thiosulfate-containing fixing bath (II) of the present invention is a thiosulfate-containing fixing bath for solubilizing bleached round steel and silver halide. This also includes bleach-fixing baths, etc.

The stabilizing treatment process 11K of the present invention can be added to other stable housing treatment processes that require a water washing process. activator, anti-pyretic agent, preservative, organic sulfur compound, onium salt,
Generally known hardeners, various metal salts, etc. are difficult to use. (9) It is preferable that the stabilization treatment process be carried out in a multi-stage tank, and that the replenisher is replenished from the last stage tank and is sequentially overflowed to the previous stage tank, using a backflow method.

Furthermore, the original Ij! In addition to the fixing bath or bleach-fixing bath, it is also possible to provide a silver-containing bath, such as a short preliminary washing, or a pollution-loading substance-containing bath, ``substantially without going through a water washing process.'' Therefore, a large amount of water washing (a replenishment amount that is more than 30 times the amount of liquid removed from the fixing bath when the photosensitive material is removed per unit area) is not performed.

A rinsing treatment or the like may be provided between the treatment using the large-scale stabilization treatment bath and the treatment solution containing an oxidizing agent.

It is undesirable to perform a 'J-so treatment or the like after treatment with a treatment solution containing an oxidizing agent, since the effect of the present invention will be weakened.

This Table 1 Processing method of the present invention can also be used for processing 11 of color paper, color reversal paper, color positive film, color negative film, color reversal film, color X-ray film, etc.

Hereinafter, the present invention will be explained in detail with reference to examples, but the embodiments of the present invention are not limited by these examples.

Example L Sakura color paper (roll form) [Konishi Roku Photo Industry @
After printing the paper, a continuous replenishment process (hereinafter referred to as running process) was carried out using an automatic printing machine (endless belt conveyance type) according to the experimental guidelines below.The processing process and composition of the processing liquid at this time is as follows.

Standard processing steps] 1. Color development 33°C 3 minutes 30 seconds 2 Bleach fixing
33℃ 1 minute 30 seconds 3, stabilization treatment 25@~
The composition of the processing solution used was as follows: 3 minutes at 30° C. and 4 minutes at 75° to 80° C. for drying.

[Coloring current tank liquid]

[Color development replenisher] (S white fixing tank solution) Fill automatic 1111111 with the above color development moderate Tanta coolant, bleach fixing Tanta tank, and the following stabilizer, partially layer the color paper, and add the above every 3 minutes from '&''. A running test was performed while replenishing the color developer replenisher, bleach-fixer replenisher I [A, B, and stable replenisher through the metering cup].
The amount of replenishment was 25-1 for each of the bleach-fixing replenishers M and B as the amount to be refilled to the 324-1 bleach-fixing tank, as the amount to be refilled to the color developing tank per 11 parts of the color paper. In addition, the stable bathtub is divided into three types (I [KI] of the flow of Kansha).
ll, the second and third stabilizing baths), the stabilizing liquid is flowed into the third stabilizing bath, the overflow from this bath is put into the second stabilizing bath, and the overflow from the second stabilizing bath is poured into the first stabilizing bath.
The treatment was carried out using a method (counter current method) in which the mixture was placed in a stable bath and overflowed from the first stable bath to the outside of the processing system.

In Experiment 1, the convergence of the processing salt is due to the fact that in Experiment 1, the total amount of bleach-fix solution replenished to the bleach-fix bath (replenisher + replenisher B in the color developing solution that adheres to the photosensitive material) is twice the tank capacity. Convergence was reached at 9 o'clock.

After experiment 2, when the amount of water and tSO replenishment reached four times the tank capacity of the stabilization bath (total of three tanks), convergence and
Closed.

Experiment 1: The stabilizing bath tank was filled with tap water, and the stabilizing solution replenisher was tap water. Color Paper 111/This paper was refilled with 5 tons of running water (normal large amount washing), and Nakura Color Paper was wedged and exposed. The eel was treated before the Lanjung treatment and when converged, and the true color, green, and red reflection eel index O0.8 to 1.8011 mm value was measured using an optical vortex meter.
The thiosulfate ion concentration in the color developing solution when the running convergence was different was measured by the potentiometric method using type mercury nitrate, and the results are shown in the table below.

Experiment 2 The stabilizing bath tank and stabilizing bath replenisher were adjusted to pH 5 and OK with 1-human xyethylidene-Ll-diphosphonic acid 1f/A, a fluorescent brightener (Chipagayi Co., Ltd., Tinopal 8FP) If/A, and potassium hydroxide. This stable replenisher was used for color paper 1D Todoroki 11100-replenishment and running processing, and convergence was reached at 9%.Similar to Experiment 1, the gamma value of each color reflectance and the thiosulfate ion in the developer were The concentrations were kept constant and are listed in Table 1 below.

Experiment 3: Continuing from Experiment 2, an oxidizing bath was set up so that the photosensitive material and the conveyor belt were immersed in it for 10 seconds between the stabilizing bath and the drying process, and a running process was carried out. The oxidation bath tank and oxidation bath replenisher are 1t/l of 1-hydroxyethylidene-Ll-diphosphonic acid, 35% hydrogen peroxide solution Sm/j, and 2f/l of sodium acetate.
1. Use potassium hydroxide to adjust the pH to 4.8K, and replenish your color paper 1-200.
When convergence is reached, as in Experiment 1, the β mm I of each color's reflection lightness and the thiosulfate ion concentration in the developer are kept constant;
In addition, the weak basic ion exchange resin and activated carbon were packed in the circulation filter of the stable bath and circulated continuously at a circulation rate of IL per minute. Treat it by removing iron ions.

Experiment 4 The maximum degree of red reflection of the samples obtained in Experiments 1 to 3 with the gamma values of each color reflection ** constant was measured, and the samples were heated with iron ferricyanide (red blood salt) asxya cool for S minutes. process,
After washing with water and drying, the maximum red reflection Il& was kept constant, and the O results and nobility differences are shown in Table 2 below.

Table-I I! -2 As is clear from Table 1 above, compared to the large amount of water washing based on the 1st standard, the washing process was simply changed to stabilizer IK, and the thiosulfate ion concentration in the 2nd color developing solution was increased. The gamma value of tometry increases and abnormalities in photographic characteristics are observed, making it impossible to put it to practical use. However, in the method of the present invention, thiosulfate ions cannot be detected, and in contrast to the gamma value, which shows an increase in gamma due to the running process even in the standard process, in the present invention, the color developing solution maintains the gamma value in the new state. ), it can be seen that it is in extremely good condition.

Furthermore, as is clear from Table 2, very slight defects in color restoration were observed in the standard treatment when washing with a large amount of water, and there were slight defects in color restoration in the comparison treatment, but the treatment method of the present invention No defective color recovery was observed in the cyan dye Roy;
It can be seen that this method is also extremely effective in preventing oxidation.

Example 2 The same experiment as in Example 1 was carried out except that the color developing tank solution and the color development @* replenishment tube of Example 1 were replaced with those shown below, and the same results were obtained.

[Color development tank liquid]

[Coloring current replenisher] Patent applicant: Konishiroku Photo Industry Co., Ltd. Attorney Patent Attorney Saka Kuchi (1 other person)

Claims (1)

[Claims] In a processing method in which a copper halide color photographic light-sensitive material is processed with a fixer or a bleach-fixer containing thiosulfate, a washing plant is substantially subdivided into a stable processing process 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that processing is carried out by using a processing solution in which an oxidizing agent is present between the stabilizing treatment process 1 and the drying process SO.