JPS60247241A - Method for processing color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain an image which can be stored stably for a long period without requiring washing by fixing a photosensitive material, introducing it into a stabilizing stage provided with many tanks, and stabilizing the material by a multistage countercurrent system while replenishing a specified amount of a stabilizing system while replenishing a specified amount of a stabilizing soln. CONSTITUTION:A color photographic sensitive silver halide material is fixed and introduced into a stabilizing stage provided with many tanks without passing through a washing stage. In the stabilizing stage, the material is stabilized by a multistage countercurrent system by which a stabilizing soln. is replenished to the final tank and allowed to overflow into the preceding tank in order. The amount of the stabilizing soln. replenished is regulated to 3-50 times the amount of a soln. brought from the preceding bath per unit area of the material to be processed, and the pH of the soln. in the first tank is adjusted to <=9. A buffer soln. so prepd. that the pH of the soln. in the final tank is kept at about 2-6.5, e.g., a sodium phosphate soln. is used as the stabilizing soln.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, it relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a method for processing a silver halide color photographic light-sensitive material, and more specifically, a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a method for processing silver halide color photographic materials capable of forming images of high quality.

Generally, color photographic images are produced by exposing a silver halide color photographic light-sensitive material to light and developing it with a color developer containing an aromatic primary amine developing agent such as paraphenylenediamine.
This can then be formed by bleaching, fixing, washing and stabilizing treatments. In the above processing process, a bleach-fixing process is usually used in which bleaching and fixing are performed simultaneously in order to speed up the process.

Color photographic images obtained through this processing process are stored for a long period of time as records, but during the storage period, the image area may fade or change color due to the influence of atmospheric humidity, temperature, or light. This often results in poor development.

<Background of the Invention> The stabilization treatment in the above-mentioned processing steps is particularly necessary to further enhance the stability of the color photographic image during long-term storage. Examples of these stabilization treatment methods include, for example: U.S. Patent No. 2,647,057, U.S. Patent No. 2,7
No. 88,274, No. 2,913,338, No. 3.
No. 667,952, No. 3,676.136, No. 2
, No. 515,121, No. 2,518,686, No. 3,140,177, No. 3,291,606, No. 3,093,479, Japanese Patent Publication No. 37-877
No. 9, Special Publication No. 1973-5735, Special Publication No. 1977-3236
No. 9, Japanese Patent Application Laid-Open No. 49-107736, specifications, and German Patent No. DT-1770074, 'r-1919
No. 045 and DT-2218387, which are known.

However, although all of the methods described are slightly effective in stabilizing color photographic images, they are by no means satisfactory, and conventional stabilization processing is a single-tank bath process suitable for short-time processing. Therefore, it was not possible to reduce the pollution load or reduce the water used for flushing.

Furthermore, a stabilization treatment method that omit the water washing step is also known, for example, as described in US Pat. No. 3,335,004, but it is a silver stabilization treatment using thiocyanate, and Because the stabilizing bath contains a large amount of sulfite, the formed image pigment is easily converted into leuco form, which has a large effect on the deterioration of color photographic images, and furthermore, at low pH, it generates sulfur dioxide gas. There is also a risk that it may cause On the other hand, in recent years, improvements have been made to photographic couplers, and as a result, the robustness of the couplers themselves has improved significantly, and as a result, the 41 stabilization process has become omitted in some processing methods that require the usual water washing process. .

However, in commonly used color photographic processing, there is still a close relationship between the stability of color photographic images during storage and the washing process. For black-and-white photographic materials in which metallic silver itself is the image, the washing time required for long-term preservation of the image is said to be 1 to 2 hours, but in the case of color photographic materials, the silver image is not bleached. Since there is no residual thiosulfate, the influence of residual thiosulfate is less than in black-and-white photographic materials, and the washing time is considerably shortened, but a certain amount of washing time is still required.

On the other hand, in recent years, photofinishers, which automatically and continuously perform general color photographic processing, have placed emphasis on environmental conservation and the saving and recovery of water and silver resources. There is a strong desire for measures such as a method of collecting water well, reducing the amount of washing water, and reusing it. For this reason, modern photographic processing processes collect silver that flows into the washing water.
Alternatively, a method has been implemented in which the pollution load in the flushing water is rendered harmless and then discharged. However, while washing water has many values and has a low concentration of ions and a low pollution load, it requires large-scale equipment for recovery and detoxification.
Five problems remain, such as the fact that it is difficult to achieve a satisfactorily high efficiency.

Therefore, as a method to solve the above problems, JP-A-55-7
Publication No. 793, Japanese Patent Application No. 54-113419, and Japanese Patent Application No. 54-148241 disclose a method of reducing washing water, a method of performing preliminary washing with a small amount of water between fixing processing and washing processing, etc. Suggestions are included.

<Technical Issues> However, a new problem is that it is necessary to drastically reduce the amount of washing water to the extent that the recovery efficiency of silver ions brought in from the fixing solution and the efficiency in making the pollution load harmless, or to improve the efficiency of the main washing. Pre-washing without increasing the amount of water or time will seriously impair the shelf life of color photographic images, and in extreme cases even short-term storage can cause yellow staining. It doesn't seem like it. Furthermore, other drawbacks include the pre-washing bath where fixing ingredients and marking ingredients are brought into the bath, and the washing treatment bath with a small amount of water, which increases the pH of the washing water, causing deposits and mold to form. This not only causes deterioration in the storage stability of photographic images, but also may cause processing failures.

The technical object of the present invention is to provide a color image stabilization processing method that overcomes these drawbacks. That is, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material by using a stabilizing bath that prevents the occurrence of precipitation during long-term standing or aging. Another object is to provide a method for processing a color photographic material capable of forming a stable color photographic image during long-term storage even if the washing step is omitted; The object of the present invention is to provide a method for processing silver chloride color photographic materials that efficiently recovers silver salts and renders the pollution load harmless.

<Means for Solving the Problem> The processing method of the present invention is to process a Hapgunkasen color photographic light-sensitive material through a stabilization process after a fixing process without substantially undergoing a water washing process, The treatment process consists of multiple tanks and is refilled using a multi-stage countercurrent method, and the replenishment amount is 3 times or more than the amount brought in from the previous bath.
The pH of the first tank among the plurality of stabilizing baths is set to 90 or less using the replenishing solution.

In the processing method of the present invention, the stabilization process is performed in a processing bath composed of multiple tanks, and the photographic material being transported is replenished in a certain amount per unit area from a subsequent processing tank. By using a countercurrent (backflow) method in which the over-two solution generated by replenishment is introduced sequentially into the former bath, the later stable bath becomes less susceptible to contamination due to fixing or bleach-fixing solution brought in. By doing so, it is possible to prevent an increase in pH and the occurrence of precipitation, and as a result, it is possible to improve the stability of color photographic images during storage without performing a washing process.
This system is designed to efficiently recover silver from a stable bath of micrometers and detoxify the pollution load. It is particularly effective in preventing precipitation in stabilizing baths.

In the present invention, performing stabilization treatment without substantially performing a water washing process means a single tank or multiple tanks in which the concentration of the fixer or bleach-fixer in the foremost tank of the stabilization treatment does not become less than 1/1000. This does not preclude the use of extremely short-time rinsing treatment using a countercurrent method, auxiliary water washing, and known washing accelerator baths.

In the present invention, the fixing process is carried out in a processing bath containing a soluble complexing agent that solubilizes μ silver halide) as a p silver halide complex salt. Also included are fixers, one-bath developer-fixers, and -bath developer-bleach-fixers.

More specifically, in general, during continuous photographic processing, fixing baths and bleach-fixing baths contain soluble silver ions in addition to the fixing agents thiosulfate and sulfite. forms a precipitate. Regarding the formation of silver sulfide, generally speaking, in solutions containing highly concentrated components such as fixers and bleach-fixers, the lower the pH, the faster the decomposition of thiosulfate; Silver formation was also said to occur quickly.

However, contrary to expectations, when the concentration of the fixer or bleach fixer is so dilute that it is mixed into the stabilizing bath involved in the processing method of the present invention, the higher the pH, the more likely silver sulfide precipitation occurs, and the final bath has a pH of 7. , 0 or more, precipitation is likely to occur (
It was found that precipitation occurs in a very short time at pH around 8.

Furthermore, in a state where silver ions are dilute, such as in the latter tank of the stabilizing bath according to the present invention, the lower the silver ion concentration is, the higher the pH is, the more likely precipitation is to occur, and the silver ion concentration is relatively high. Furthermore, it has also become clear that precipitation is unlikely to occur even when the pH exceeds 7.0, as in the first-stage tank of the stabilizing bath according to the present invention.

The present invention was made based on the above-mentioned fact, and in the first stage bath, the pH is relatively high and the silver 9- ion concentration is high (in the second stage bath, the silver ion concentration is more diluted and the pH is increased). is maintained in the range of 20 to 65.
Since the stabilization treatment process is composed of multiple tanks and replenishment is carried out using a countercurrent method, it has become possible to prevent the occurrence of sediment in all stabilization treatment baths.

The final tank of the stabilizing bath according to the present invention preferably has a pH in the range of 20 to 65 and has a buffering capacity in order to prevent precipitation and provide stability during storage of color photographic images. In this case, the buffering capacity is necessary to suppress the increase in pH caused by the fixing solution or bleach-fixing solution mixed into the stabilizing bath from the fixing bath or bleach-fixing bath, which is a prebath of the stabilizing bath, during continuous processing. Specifically, a solution containing 3 parts of the stable bath and 1 part of the mixed liquid from the previous bath was heated at 25°0 for 5 days.
It is used to suppress the pH to at least 90 or less, preferably 8.0 or less when stored in an open state.

In the stabilization treatment method of the present invention, as described above, the stabilizing bath is composed of multiple tanks, and the replenisher is replenished from the latter tank and sequentially overflows into the front tank, and the overflow from the foremost cypress is discarded. The silver is recovered and detoxified.

Therefore, the higher the position of the stable bathtub, the higher the p of the bath liquid.
Since H is strongly influenced by the fixing solution or bleach-fixing solution in the pre-bath, the pH of the stabilizing solution in the pre-bath with high silver ion concentration is not necessarily within the range of 20 to 65, which is the preferred pH value for the final bath. There is no need for the pH to be higher than 90; rather, it is preferable to have a higher pH in order to prevent precipitation, and there is no problem as long as the pH is at least 90 or less. Therefore, in the final bath, which has a very low silver ion concentration, a pH of 2.0 is used to prevent precipitation and to stabilize color photographic images during storage.
It is preferable to maintain the pH at pH 3.0 to 6.5, with a particularly preferable range being pH 3.0 to 6.5. When the pH is outside this range,
If it is higher or lower, there is a strong tendency for precipitation to occur in the final tank or for the deterioration of color photographic images to increase during storage.

For the above-mentioned reasons, the stabilizing bath according to the present invention is composed of multiple tanks and is of a long-bath processing type. It is closely related to the relationship between the quantity and the amount of replenishment; the smaller the ratio of the amount of replenishment to the amount brought in, the more cypresses are needed, and the larger the ratio, that is, the larger the amount of replenishment, the fewer the number of tanks. It will be over.

Generally, when the amount of replenishment is 3 to 5 times the amount brought in, it is necessary to process K in 9 to 10 tanks, and when the amount is 50 times, the purpose can be achieved with treatment in 3 to 4 tanks. can.

The stabilizing bath according to the present invention has a pH of 20 to 6 in the final tank of the stabilizing bath.
．． Any buffer adjusted to maintain the pH within the range of 5 can be used, and various buffers can be used.
Examples include monocarboxylate, dicarboxylate, polycarboxylate, oxycarboxylate, amino acid, aminocarboxylate, primary phosphate, secondary phosphate, tertiary phosphate, sodium hydroxide, potassium hydroxide, etc. be able to. Furthermore, it is preferable to add various chelating agents as well. Examples of these include aminopolycarboxylate, 7
These include minopolyphosphonic acid, phosphonocarboxylic acid, alkyritene diphosphonic acid, phoryphosphate, hiruric acid, metaphosphoric acid, and gluconate. Among these, flukylidene diphosphonic acid as used in the following examples is preferably used.

Other commonly known stabilizing bath additives include, for example, fluorescent brighteners, surfactants, anti-pie agents, preservatives, organic sulfur compounds, onium salts, hardeners, and various metal salts. For example, it is preferable to use benzoic acid as shown in the Examples. The amount of these compounds to be added may be determined within a range that is necessary to maintain the pH level of the stabilizing bath according to the present invention and does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. There is no problem in using such combinations. However, according to the treatment method of the present invention, silver can be efficiently recovered and rendered harmless, and from the viewpoint of pollution load, cost control, etc., it is preferable to dilute the silver as long as the buffering capacity is sufficient.

13- The temperature of the stabilizing bath treatment is 15°C to 60°C, preferably 20°C.
The temperature range is preferably from ℃ to 45℃. In addition, from the viewpoint of rapid processing, a short processing time is preferable, but it is usually 20 seconds to 10 minutes.
The most preferable time is 1 minute to 5 minutes, and it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time.

After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary.

The processing method of the present invention as described above can also be used to process color paper, color reversal paper, color positive film, color negative film, color reversal film, color X-ray film, and the like.

Example 1 Sakura Power Paper (Pole shape) (Konishi Roku Photo Industry Co., Ltd.)
After printing, continuous replenishment processing (referred to as running processing) was performed using an automatic processor.

The treatment steps and composition of the treatment liquid at this time are as follows. be.

Standard processing step 1, color development 33°C 3 minutes 30 seconds 2 bleach-fixing 33°C 1 minute 30 seconds 3, stabilization 25° 0-30°C 3 minutes 4, drying 75° 0-80°C approximately 2 minutes Processing solution Composition (color developing tank liquid) Benzyl alcohol 15ml Ethylene glycol 15 Potassium sulfite resistant 2.017 Potassium bromide 0.7g Sodium chloride 029 Potassium carbonate 30.0, ii' Hydroxylamine sulfate 3. OI phosphoric acid (TPPS) 2.5. 93-Methyl-4-7minor N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.51/Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1. Oi Potassium hydroxide 209 Add water to make 1 NO.

(Color development replenisher) Benzylfurfur 20m Ethylene glycol 201 Potassium sulfite 3.0g Potassium carbonate 30.0 & Hydroxylamine sulfate tJK 4.077 Jelly Phosphoric acid (TPPS) 3.0.93-Methyl-4-amino-
N-ethyl-N=(β-methanesulfone 7midoethyl)
- Aniline sulfate 7.0.9 Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.577 Potassium hydroxide 3.0, p Water is added to bring the total amount to 11.

(Bleach-fix tank solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 J Ethylenedi7minetetraacetic acid 3I! Ammonium thiosulfate (70% solution) 10011/Ammonium sulfite (40% solution) 27.511+7 Adjust to pH 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

(Bleach-fixing replenisher A) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 260, P Potassium carbonate 42J Add water to bring the total volume to 11.

The pH of this solution is 6.7±01.

(Bleach-fix replenisher B) Ammonium thiosulfate (70% solution) 5ooy Ammonium sulfite (40% solution) 250ml ethylenedi7
Minetetraacetic acid 1711 Glacial acetic acid 85m Add water to bring the total volume to 11.

The pH of this solution is 46±0.1.

Fill an automatic processor with the above color developing tank solution, bleach-fixing tank solution and the following stabilizer, and add the above color developing replenisher and bleach-fixing replenisher A and B every 3 minutes while processing the color paper. A running test was conducted while replenishing constant replenishment solution through a metering cup. The amount of replenishment is color paper 1. The amount of replenishment to the color developing tank per i is 32411/.

Bleach-fix replenisher A and B as replenishment amounts to the bleach-fix tank
Each was 25m+7.

For the stabilization treatment, the stabilization treatment baths of the automatic developing machine were configured into 3 hinoki, 6 hinoki, and 9 hinoki, and were modified so that continuous processing could be performed. The stabilization processing baths of each automatic developing machine are arranged in the direction of the flow of the photosensitive material, consisting of the first tank to the third tank, the first tank to the sixth tank, and the first tank to the ninth tank, and a final tank. A multi-tank countercurrent system was adopted in which the overflow from the final tank was made to flow into the cypress in the previous stage, and the overflow liquid was also allowed to flow into the cypress in the previous stage. As a comparative treatment, an automatic developing machine having a stabilization treatment bath consisting of one cypress was used. Continuous processing was carried out until the total amount of bleach-fix solutions A and H used became the same as the tank capacity of the bleach-fix solution, and then the following stabilizing solution was used.

18- Measure the pH of the stabilizing solution in the stabilization treatment bath, visually observe the presence or absence of precipitation, and leave the sample obtained after treatment at 60°C and 80% relative humidity for 6 weeks to reach the lowest blue concentration. It was measured. The results are shown in Table 1. In addition, color paper 1r
r? The amount of bleach-fix solution to be carried into the stabilizing solution is 5011L.
It was l.

Stabilizer-1 1-Hytroxyethylidene-1,1-diphosphonic acid 2
g Glacial acetic acid 2d Formaldehyde boric acid 5g 1.2-Benzisothiazoline 05y Benzoic acid 0.
5, S+ It was brought to 11j with water, and the pH was adjusted to 40 with sodium hydroxide.

19- As is clear from Table 1 above, in the stabilization treatments not according to the present invention (Comparison-1 to Comparison-5), since the stabilization bath configuration is one tank, the amount of stabilizing solution replenishment is different from that according to the present invention. Even if it is within the included range or outside the scope of the present invention, the yellow stain indicated by the lowest blue concentration is high, and furthermore, the renewal rate of the tank fluid is poor and precipitation of silver sulfide and iron hydroxide occurs. It stuck on the color paper and caused a malfunction. Furthermore, even if the stabilizing bath was changed to 3 ia or 6 baths, the amount of replenishment of the stabilizing solution other than the one according to the present invention resulted in the occurrence of significant Yep-staining and precipitation.

On the other hand, stabilization treatment according to the present invention (present invention-1 to present invention-
7), the yellow stain indicated as the lowest blue concentration was low in all cases, and no precipitation or mold was observed.

In the experiment of this example (invention-3), the stable replenisher was replenished in divided amounts of 2,501 m to the 6th cypress and 250 m to the 4th cypress, but the effect did not substantially change.

In addition to this example, the color negative was processed using the processing process Sakura C.
After the fixing treatment of NK-4, a stabilization treatment consisting of a 6-dan structure was carried out in the same manner as in the experiment of this example (present invention-3), and the same effect was obtained. Furthermore, in the treatment according to the present invention of this example (present invention-1 to present invention-7), after stabilization treatment 2
Although rinsing (Japanese cedar) was performed for 0 seconds, no difference was observed regarding yellow stain.

Example 2 Using color paper under the same conditions as the experiment in Example 1 (invention-3), continuous processing was carried out for 3 times using an automatic processor until the total amount of bleach-fix replenisher became equal to the bleach-fix tank capacity.
I went for 0 days.

As a stabilizing solution, the following components were added per 11 parts water.

Stabilizer (replenisher) Citric acid 3. ! i+ Sodium citrate II Sodium benzoate 0.21i 1-hydroxyethylidene-1,1'-diphosphonic acid
059 2-Methylisothiazolin-3-one 0.2. ! i'
The pH was adjusted to 1.5, 4.0, 6.0, and 7.5 K using sodium hydroxide, glacial acetic acid, and sulfuric acid, respectively.

The replenisher was used as the tank solution for stabilization processing, and the amount of replenishment was 500 m/11 photosensitive materials.After continuous processing, the pH values from the first to the sixth hinoki were measured, and at the same time, the precipitation was measured. The occurrence was visually observed. Furthermore, each sample after treatment was stored at 60° C. with a relative humidity of 80% for one week, the lowest blue density was stored for two weeks, and the maximum red density was measured.

27 23-2 Table 24- As is clear from Table 2, in Examples 8 and 11, precipitation was observed in a part of the stabilizing bath due to the relationship between the concentration of metal ions carried into the stabilizing solution and the pH. Even in this case, no precipitation was observed in the front tank.

In addition, if the residence time of the stabilizing solution is long due to continuous processing in small quantities, it is possible to add an isothiazolin-3-one type compound or 1-pomo-3-I to the stabilizing solution of the present invention.
: The effect of anti-mold agents such as lρ-5,5-dimethylhydantoin was also observed.

25-

Claims (1)

[Claims] In a processing method in which a silver halide color photographic light-sensitive material is subjected to a stabilization process after a fixing process without substantially undergoing a water washing process, the stabilization process consists of multiple tanks and is replenished in a multistage countercurrent system. In this case, the replenishment amount is 3 times the amount brought in from the pre-bath per unit area of the photosensitive material to be processed.
The pH of the first tank among the multiple tanks is 9.
A method for processing a silver halide color photographic material, characterized in that the silver halide color is 0 or less.