JPH052252A - Treating method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a treating method by which stable photographic characteristics can be maintained even when the amt. of waste liquid of a treating liquid is largely decresed or completely eliminated, and especially to obtain the method effective for stability in the treating for a high silver chloride color phtographic sensitive material. CONSTITUTION:A silver halide photographic sensitive material exposed to light is continuously treated while a replenisher is added. This treatment features in that when the lever of the liquid in the treating tank lowers by a certain amt., not the replenisher but a new liquid (liquid in a tank for new liquid) is added to the treating tank to return the liquid lever to the standard level.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method of a silver halide photographic light-sensitive material, and provides a processing method which is not preferable in terms of environmental protection, in which the discharge amount (waste liquid amount) of the processing liquid is reduced or eliminated, and is very stable. To a processing method for providing the described photographic properties.

[0002]

2. Description of the Related Art In a method for processing a silver halide photographic light-sensitive material, particularly in a large-sized processing machine, in the case of continuous processing, a tank solution is contained in the processing machine, and the activity depends on the processing amount of the light-sensitive material. A method of replenishing a high replenisher is generally used. At this time, the tank liquid overflows due to the amount of the replenishing liquid (overflow liquid), and this liquid is discharged out of the system. The discharged liquid is collected and treated as waste liquid, but these processed liquids have a large pollution load value, are not preferable in terms of environmental protection, and the collection and delivery cost for collecting them cannot be ignored.

Therefore, various techniques for reducing the amount of waste liquid have been studied so far. As an example, various methods have been studied for removing accumulated components from the overflow liquid, adding additional deficient components as needed, and reusing them as a replenishing liquid. These methods are generally called a method of regenerating a processing solution and are applied to various developing solutions, bleaching solutions, fixing solutions and the like.
However, in the regeneration method, the quality of the replenishment replenisher is very difficult to control because it is greatly affected by the history of the overflow, and the treatment liquid requires high quality control by various analyzes. It can be used only in a laboratory having technical capabilities. Moreover, its quality is generally unstable as compared with a non-reproducing system, and the labor for reproducing is also required, so that the implementation destination is greatly restricted, so it cannot be said to be a general-purpose technique.

On the other hand, as a technique for reducing the amount of waste liquid, a technique for reducing the replenishment amount itself is known. In order to reduce the amount of replenishment, generally, the technical problems such as how to overcome the influence of accumulated components, how to make a concentrated replenisher, how to improve the stability of the processing solution, etc. are solved. It is necessary. For example, a technique for reducing the replenishment amount of the color developing solution is disclosed in JP-A-61-70552 and JP-A-1-105948.
No. etc. It can be said that such a low replenishment process is more preferable because it has high versatility because no special technique is required if the amount of waste liquid is equal to or less than that of the regeneration process.

In particular, as in the above-mentioned reference, in the color developing solution in the first bath in the color processing step, the replenishment amount is equal to the carry-over amount (carry-out amount), and water is added to the evaporated portion. By correcting with
Theoretically, it is possible to process without overflow, that is, without waste liquid, and it is considered to be the limit of low replenishment.

[0006]

However, when the ultra-low replenishment process aiming at no waste liquid as described above is performed, an overflow liquid of the color developer is generated, or conversely, the liquid level of the processing tank is lowered. However, it was impossible to carry out a stable treatment. In particular, the decrease in the liquid level in the processing tank is directly connected to the fluctuation of the processing time (shortening the processing time), which not only impairs the quality but also adversely affects the heater and the circulation system of the processing machine. As a result of examination of the cause, it was found that the carry amount varied. That is, in particular, in a processor that conveys a light-sensitive material using a leader belt, there is carryover by driving the leader belt (1 to 3 ml / m is carried over, depending on the material and linear velocity). However, since the leader belt does not react in the treatment liquid, it is generally not replenished at all when the leader belt is conveyed. In such a situation, the processing machine is driven in various states in the photo lab. That is, when only the drive is operated and the photosensitive material is not processed, when one row of photosensitive material is mounted on the leader belt, when two rows of photosensitive material are mounted on the leader belt, etc. It was found that the amount of carry of the leader belt was different in processing the light-sensitive material, and as a result, the carry-over amount was different.

Therefore, when performing the ultra-low replenishment process as described above, how to keep the tank liquid level constant is an important issue. Therefore, an object of the present invention is to provide a treatment method in which the discharge amount of the treatment liquid is greatly reduced, and to provide a treatment method whose performance is stable despite the low replenishment amount.

[0008]

It has been found that the above object can be achieved by the following processing method. That is, in the processing method of continuously processing the imagewise exposed silver halide photographic light-sensitive material while replenishing the replenishing solution, the new solution (new tank solution) is replenished when the liquid level in the processing tank drops by a certain amount. And a method for processing a silver halide photographic light-sensitive material.

According to this method, an imagewise exposed silver halide photographic light-sensitive material is replenished in a processing tank (processing tank) with a predetermined amount of replenisher per unit area of the photographic light-sensitive material to be processed. A method for processing a photographic light-sensitive material, which is more effective by adding a new liquid (new tank liquid) to the processing tank when the liquid level of the processing liquid in the processing tank is lowered by a certain amount. It can be carried out. Here, when the liquid level has decreased by a certain amount, it is preferable to detect the decreased amount and automatically supply the new liquid to the processing tank separately from the replenishing liquid.

In the present invention, the new liquid or the new tank liquid is
It means the treatment liquid to be added to the treatment tank or treatment tank when starting the treatment, and after that, that is, after the treatment is started,
It is called a working solution. Further, the conventional replenishing tank solution or replenishing solution is also referred to as a replenishing solution in the present invention. In the present invention, the new tank liquid is also used in the present invention to add it to the processing tank and restore the liquid surface to a standard state when the liquid surface of the processing liquid is lowered. The tank liquid is a processing liquid contained in the processing tank, and includes a new tank liquid and a running liquid.

The processing machine used in the method of the present invention includes a processing tank, a replenishing tank, a tank for new liquid, a means for detecting the liquid level of the processing tank, and a means for supplying new liquid (new tank liquid) to the processing tank. A photographic processor characterized by having the following is preferable. In the processing method of the present invention, it can be applied to any processing bath (for example, color development, black-and-white development, bleaching, fixing, bleach-fixing, stabilization, etc.). Is most effective for use in the first bath, and more specifically, it is effective for a black-and-white developing solution in a black-and-white processing step or a color reversal processing step, or a color developing solution in a color processing step. Further, it is preferably applied to a color print material system having a relatively large average carryover amount. The carry-over amount here means the running liquid (workin) carried out from the processing tank to the next step by a conveyance means such as a photosensitive material and a leader belt.
g solution). In the first bath, if the average replenishment amount is less than the average carryover amount, there is also the effect of evaporation and the like, and virtually no emission processing is theoretically possible.
However, as described above, since the carry-over amount changes according to the processing situation, how to control the overflow amount and the liquid level down is an important issue.

The average carry-over amount is a value obtained by dividing the amount of processing liquid carried out to the next tank (next tank) in a certain time by the amount (m ² ) of photographic light-sensitive material developed in that time. Is. Here, the average carryover amount can be easily obtained by those skilled in the art. For example, the photosensitive material being processed, the method of taking out the leader belt and measuring the increase in weight, the method of subtracting the total amount of overflow from the total amount of replenishment per unit time, and the unit amount of processing when the photosensitive material was processed without replenishment. Can be performed by a method of determining the liquid level decrease amount of.

As described above, in order to maintain a stable non-discharge state at all times, it is preferable to set the replenishment amount to be smaller than the average carryover amount. For example, it is preferably 0.99 to 0.70 times the average carryover amount and 0.95 to 0.70.
An 80-fold amount is particularly preferable. Specifically, it is 30 to 90 ml, preferably 40 to 85 ml per 1 m ² of the light-sensitive material.
The liquid level can be controlled by automatically replenishing the liquid level lowering portion with a new liquid (new tank liquid). With respect to the decrease in the liquid level, the running liquid is diluted more than necessary by simply correcting the water, which is not preferable in terms of photographic characteristics.

As described above, the new tank liquid is a processing liquid which is capable of obtaining photographic performance extremely close to the photographic characteristics obtained with a working solution and is newly prepared. In the present invention, the composition of the replenishing liquid and the new tank liquid are different, and the following are preferable. For example, with respect to the replenisher for the color developing solution, the concentration of the main agent and the preservative (for example, sulfite, hydroxylamine or its derivative) is high,
The pH is high pH. Also, the halide concentration is low. Here, the difference in the concentration of the main agent is preferably 1 g / liter or more, the difference in the preservative concentration is preferably 1 g / liter or more, the pH difference is preferably 0.1 or more, and the halide concentration difference is preferably It is 0.02 mol / liter or more.

The replenishing method of the present invention is a method using at least two kinds of liquids, a replenishing liquid and a new tank liquid. The replenisher is replenished according to the amount when the light-sensitive material is developed. Therefore, in the present invention, replenishment is not normally performed when the automatic processor is stopped. In an automatic developing machine, generally, even when the light-sensitive material is not subjected to development processing, a conveying means such as a leader belt continues to move without stopping. Therefore, the replenisher is mainly used to supplement the active components in each processing solution consumed by the processing, is absorbed or adsorbed by the photosensitive material to be processed, and is lost by adsorption to the conveying means or its guide. It is added to each treatment tank to supplement the treatment liquid. The replenisher can be added to the treatment tank continuously or intermittently.

However, even if the above replenisher is added to the processing tank, the level of the processing liquid in the processing tank actually decreases. It is considered that the decrease of the processing liquid level is due to the variation of the carry-over amount due to the photosensitive material or the conveying means and the evaporation of the processing liquid. From the above, the addition of the new tank liquid to the processing tank compensates for the decrease in the processing liquid level in the processing tank, and is added to the processing tank according to the amount of the photosensitive material to be processed like the replenishing liquid. Not a thing. That is, the addition of the new tank liquid is different in purpose and effect from the replenishment of the replenisher. Further, when the development processing of the light-sensitive material becomes a discontinuous processing, the problem of the liquid level lowering becomes more remarkable, and in this case, it is effective to apply the method of the present invention.

The processing liquid of the present invention will be described in detail below. As the developing solution of the present invention, a black and white developing solution and a color developing solution can be used. Examples of black and white developing agents include dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol. Known developing agents can be used alone or in combination.

As the color developing solution (color developing solution), an aromatic primary amine type color developing agent is preferably used. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include -β-methanesulfonamidoethylaniline, 4-amino-N-ethyl-N-hydroxyethylaniline, and their sulfates, hydrochlorides, phosphates, oxalates, and p-toluenesulfonate. Two or more kinds of these main drugs can be used in combination depending on the purpose.

Various preservatives (antioxidants) can be used in the developer of the present invention. It is generally known to use sulfite and hydroxylamine, but various organic preservatives can also be used. Preferred organic preservatives include diethylhydroxylamine, N, N-dimethoxyethylhydroxylamine, N, N-disulfoethylhydroxylamine, N, N-dicarboxyethylhydroxylamine, N, N-diphosphonoethylhydroxyl. Hydroxylamine derivatives such as amines, N, N-dicarboxymethylhydrazine, sulfoethylhydrazine,
Hydrazines such as sulfopropylhydrazine, alkanolamines such as triethanolamine and diethanolamine, and catechols such as catechol-3,5-disulfonic acid and catechol-3,5,6-trisulfonic acid can be preferably used. The amount of these preservatives added is 0.1 g to 30 g, preferably 0.5 to 15 g, per 1 L of the developer.
It is g.

In the replenishing method as in the present invention, the composition of the color developing solution to be used is more effective when the content of sulfite is smaller. That is, those containing substantially no sulfite are preferable, and those containing a small amount of unsubstituted hydroxylamine are more preferable, and those containing substantially no hydroxylamine are more effective. PH of the developer used in the present invention
Preferably pH 9-12, more preferably pH 9.5-11
Is. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate,
Borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2 -Amino-2-methyl, 1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonate, phosphate, tetraborate, hydroxybenzoate, solubility, pH
It has excellent buffering ability in the high pH range of 9.0 or higher, has no adverse effect on photographic performance (fogging, etc.) even when added to a developing solution, and is inexpensive, and uses these buffering agents. Is particularly preferred.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffering agent added to the developer is preferably 0.1 mol / 1 or more, and particularly 0.1 mol / 1 to 0.1.
It is preferably 4 mol / 1. In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the developer or for improving the stability of the developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,
N, N-trimethylenephosphonic acid, ethylenediamine-
N, N, N ', N'-tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane, 1,2 , 4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid etc. are mentioned. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the developing solution. For example, 0.1 to 1 per liter
It is about 0 g.

If desired, any development accelerator can be added to the developer. As a development accelerator, Japanese Patent Publication No. 37-16
088, 37-5987, 38-7826,
Thioether compounds represented by U.S. Pat. Nos. 4,4,12,380, 45,90,19 and U.S. Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-15554.
P-phenylenediamine compounds represented by JP-A No. 50-137729, JP-B-44-30074,
Quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, US Pat.
4,903, 3,128,182, 4,230,796, 3,253,
919, Japanese Examined Patent Publication No. 41-11431, U.S. Pat. No. 2,482,
Amine compounds described in 546, 2,596,926 and 3,582,346, and JP-B-37-16088, 42-
25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-
11431, 42-23883 and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

Particularly, in the present invention, for the purpose of reducing stain and enhancing color developability, preferably chlorine ion is adjusted to 0.
035 mol / liter or more, and more preferably 0.04 to 0.
The case of containing 15 mol / liter is particularly preferable. Here, chlorine ions may be added directly to the developing solution or may be eluted from the light-sensitive material into the developing solution during the development processing. When added directly to the developing solution, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Sodium chloride and potassium chloride. Further, it may be supplied from an optical brightening agent added to the developing solution.

As bromine ion supplying substances, sodium bromine, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, odor Thallium bromide may be mentioned, of which potassium bromide and sodium bromide are preferred. When it is eluted from the light-sensitive material during the development processing, both chlorine ion and bromine ion may be supplied from the emulsion or may be supplied from other than the emulsion.

The developing solution applicable to the present invention preferably contains a fluorescent whitening agent. As an optical brightener,
4,4'-diamino-2,2'-disulfostilbene compound is preferred. The addition amount is 0 to 5 g / liter, preferably 0.1 to 4 g / liter. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the developing solution applicable to the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the replenishment amount is small, but 10 to ⁴ per 1 m ^{2 of} light-sensitive material
00 ml is suitable, preferably 20 to 300 ml.
More preferably 30 ml to 90 ml, most preferably 40 ml
~ 85 ml.

Next, the desilvering process applicable to the present invention will be described. In the desilvering step, generally, any step such as a fixing step, a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used. The bleaching solution, the bleach-fixing solution and the fixing solution applicable to the present invention will be described below. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids, aminopolycarboxylic acids). Phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid and the like) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of ethylene diamine tetraacetic acid, diethylenetriamine pentaacetic acid, 1,3-diaminopropane tetraacetic acid, propylene Examples thereof include diamine tetraacetic acid, nitrilotriacetic acid, cyclohexane diamine tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thylium or ammonium salts. Among these compounds, iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenedriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate and ferric phosphate.
A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid. In addition, the chelating agent may be used in excess of the amount required to form the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, U.S. Pat. No. 3,893,858, German Patent No. 1,290,812, Japanese Patent Laid-Open No. 53-9563.
No. 0, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-45-8506.
No. 52-20832 and 53-32735.
And thiourea compounds described in U.S. Pat. No. 3,706,561 and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or iodide (eg, ammonium iodide) or the like. If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
It is possible to add one or more inorganic acids having pH buffering ability such as citric acid, sodium citrate, tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide solubilizers such as thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9. Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution and fixing solution are used as preservatives such as sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.). Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound is preferably contained. These compounds are preferably contained in an amount of about 0.02 to 0.05 mol / liter in terms of sulfite ion, and more preferably 0.04 to 0.40 mol / liter.

As the preservative, a sulfite is generally added, but ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound or the like may be added. Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added if necessary. After desilvering processing such as fixing or bleach-fixing, washing and / or stabilization processing is generally performed. The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pilots (Journal of the Society of Motion Pi
cture and Television Engineers) Volume 64, p.248
~ 253 (May 1955 issue). Normally, the number of stages in the multi-stage countercurrent system is 2
6 is preferable, and 2 to 4 is particularly preferable.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced, and for example, 0.5 liter to 1 per 1 m ^{2 of the} light-sensitive material.
Although it is possible to be less than 1 liter, the effect of the present invention is remarkable, but due to the increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. As a solution to such a problem, Japanese Unexamined Patent Application Publication No. Sho 62-62
The method of reducing calcium and magnesium described in -288838 can be used very effectively.
Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, 61-120145.
Chlorinated bactericides such as sodium chlorinated isothianeurate described in JP-A No. 61-267761, benzotriazole described in JP-A No. 61-267761, copper ion and others Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal" (1086) Sankyo Publishing, "Sterilization, sterilization, and antifungal technology of microorganisms" edited by Sanitary Technology Association (1982) Industrial Technology Association, "Antibacterial and Antifungal Agent Encyclopedia" (1986) edited by Japan Society for Antibacterial and Antifungal Agents,
It is also possible to use the bactericide described in. Further, in the wash water, a surfactant as a draining agent and an E as a water softener
A chelating agent represented by DTA can be used.

It is also possible to carry out the treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surface active agent, an optical brightening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a water washing step, JP-A-57-8543 and JP-A-58-14834,
All known methods described in JP-A No. 60-220345 can be used. In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound. A so-called rinse solution is also used as a washing solution or a stabilizing solution used after the desilvering process. The pH of the washing step or stabilizing step is preferably 4-10, more preferably 5-8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. It is preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The replenishment amount is
A smaller amount is preferable from the viewpoints of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount per unit area from the pre-bath. Or 1 per 1 m ^{2 of} light-sensitive material
It is less than liter, preferably less than 500 ml. Replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, a multi-stage countercurrent method is used to reduce the overflow of washing water into the fixing bath or bleach-fixing bath, which is the preceding bath, and replenish the fixing bath or bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid. Can be mentioned.

Next, the processor (automatic processor) used in the present invention will be described in detail. The processor used for the silver halide photosensitive material conveys the photosensitive material by various methods. Typical examples include conveyance by a facing roller (sheet developing machine), conveyance by a leader belt, and conveyance by a clip. The present invention can be applied to any processing machine, but as described above, it is particularly effective in a processing machine that employs a leader belt transport system in which the carry-over amount easily changes. Typical examples of the leader belt transport include a so-called cine-type processor that directly bonds the photosensitive material to the leader belt and transports it, and a processor that attaches a clip to the leader belt and transports the photosensitive material between the clips. Comparing the former with the latter, the former can handle only one row with one leader belt, while the latter can handle more than two rows by attaching clips to the left and right of the leader belt. Is. In the present invention, application to both processors is preferred.

Typical examples of the processor will be given below, but the present invention is not limited to these. Fuji Color Negative Film Processor (Fuji Photo Film Co., Ltd.) FNCP600 FNCP900 Fuji Color Paper Processor (Fuji Photo Film Co., Ltd.)
FPRP406 FPRP409 FPRP412 In this processing machine, it is preferable to have a device for detecting when the liquid level of the processing tank (tank liquid level) has decreased by a certain amount. Specifically, a liquid level sensor represented by a float switch or the like. Is preferred. In this case, it is preferable that the position of the liquid level sensor is set to a position at which the liquid level is lowered by 1% to 20% of the tank capacity, more preferably 2% to 20%, further preferably 2% to 10%. %, Most preferably 4% to 10%. If the set position is too high (too small than the above value, malfunction tends to occur, and if it is too low, photographic characteristics may fluctuate and the heater and circulatory system may be adversely affected. For example, the following volumes are used, and the standard volume is used if not.

The present invention is based on the operation of the above sensor,
New tank liquid is automatically added to the tank. It is preferable that the additional amount is made up of the liquid level lowering portion. In addition, it is preferable to prepare a stock tank for the new tank liquid separately. To prepare the new tank liquid, melted in a separate tank may be poured into the stock tank. Alternatively, it may be automatically prepared and injected into the stock tank. When a new tank liquid is automatically prepared, it may be directly replenished to the processing tank (processing tank). In the present invention, the most preferable specification is to provide a stock tank, and if there is overflow liquid, store it once in the stock tank and add a new tank liquid to this to replenish the new tank for liquid level correction. Since the amount of liquid used is reduced and the amount of waste liquid is also reduced, the running cost is reduced and the method is preferable in terms of environmental protection. For the purpose of preventing oxidation, it is preferable to use a floating lid, floating ball or the like in the stock tank. The size of the stock tank is 0.01 to 0.5 of the tank capacity of the processor.
It is about double, preferably about 0.05 to 0.2 times.

From the above, according to the method of the present invention, the image-wise exposed silver halide photosensitive material conveying belt is circulated through the processing tank, the photographic photosensitive material is carried on the belt, and the photograph conveyed by the belt is conveyed. It is preferably applied to a method of processing a light-sensitive material in a processing liquid while supplementing a predetermined amount of replenishing liquid per unit area of the light-sensitive material to be processed. Here, the processing bath can also be composed of a developing bath, a desilvering bath, a washing bath and / or a stabilizing bath.

The light-sensitive material used in the present invention will be described. As the light-sensitive material of the present invention, any material can be used as long as it is a silver halide photographic light-sensitive material, but a silver halide color photographic light-sensitive material containing a high silver chloride emulsion is most preferable in that the replenishment amount can be remarkably reduced. A preferred color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support. . In general color photographic printing paper, it is normal that the color printing paper is coated on the support in the above order, but the order may be different from this. Also, an infrared sensitive silver halide emulsion layer can be used in place of at least one of the above emulsion layers. In these light-sensitive emulsion layers, silver halide emulsions having sensitivity in respective wavelength ranges, dyes having a complementary color relationship with the light to be exposed-that is, yellow for blue,
Color reproduction by the subtractive method can be performed by including a so-called color coupler that forms magenta for green and cyan for red. However, the photosensitive layer and the coloring hue of the coupler may not have the above correspondence.

The halogen composition of the silver halide emulsion used in the present invention may be any composition, but is substantially silver iodide-free silver chlorobromide containing 80 mol% or more of silver chloride. Is particularly preferable in terms of constituting the object of the present invention. The term "substantially free of silver iodide" means that the silver iodide content is 1.0 mol% or less, preferably 0.2.
It means less than or equal to mol%. If the silver chloride content is low or if the silver iodide content is higher than this standard, the developing speed is slow and it cannot be applied to rapid processing. Therefore,
The higher the silver chloride content, the better. That is, 90 mol% or more is preferable, and 95 mol% or more is further preferable. It is also preferable to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 98
An emulsion of substantially pure silver chloride having a mol% to 99.9 mol% is also preferably used. However, the use of pure pure silver chloride emulsion may be disadvantageous in obtaining high sensitivity and preventing fog which occurs when pressure is applied to the light-sensitive material.

The halogen composition of the emulsion may be different or the same between the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, the core inside the silver halide grains and the shell surrounding it ( Shell) A so-called layered structure particle having a different halogen composition with [one or more layers], or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (edge or corner of the particle when present on the particle surface) Alternatively, particles having a structure in which parts having different compositions are bonded on the surface can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion preferably has a structure having a localized layer of silver bromide in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized layer is preferably at least 10 mol% in terms of silver bromide content, and 20 mol%
It is more preferable that the number exceeds. These localized layers can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example is a layer epitaxially grown on the corners of the particles.

On the other hand, from the standpoint that the effect of the present invention is better exhibited, it is also possible to use grains of a uniform structure having a small distribution of halogen composition in grains in a high silver chloride emulsion having a silver chloride content of 90 mol% or more. This is preferably done. The coated silver amount of the silver halide emulsion used in the present invention is preferably 0.80 g or less per 1 m ² of the light-sensitive material from the viewpoint of reducing the replenishing amount, preventing fog and reducing photographic fluctuation. In particular,
It is preferably 0.75 g or less, more preferably 0.70 g or less, per m ^{2 of the} light-sensitive material.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is determined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called dispersion coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The shape of silver halide grains contained in a photographic emulsion is irregular, such as cubic, tetradecahedral or octahedral, having a regular crystal form, spherical, tabular or the like. Those having an irregular crystal form or those having a composite form thereof can be used.
It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can.
In particular, the above Group VIII elements can be preferably used.
The amount of these compounds added may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-21.
Those described in the lower right column on page 18 to the upper right column on page 22 of the specification of No. 5272 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity. The spectral sensitizing dye used at this time is, for example, Heter by FM Harmer.
ocyclic compounds-Cyanine dyes and related compo
unds (John Wiley & Sons [New York, Londun],
1964). As specific examples of the compound and the spectral sensitization method, those described in the above-mentioned JP-A No. 62-215272, page 22, upper right column to page 38 are preferably used.

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. The emulsion used in the present invention may be any type of so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of a grain, or so-called surface latent image type emulsion in which a latent image is mainly formed inside a grain. Is also good.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is coupled with an oxidant of an aromatic amine color developing agent to form a yellow coupler, a magenta coupler, and a yellow coupler, and magenta coupler, respectively. And cyan couplers are commonly used. Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are represented by the following general formula (C-
I), (C-II), (M-I), (M-II) and (Y).

[0056]

[Chemical 1]

[0057]

[Chemical 2]

[0058]

[Chemical 3]

In general formulas (C-I) and (C-II)
And R₁, R₂And R_FourIs a substituted or unsubstituted fat
Represents a group, aromatic or heterocyclic group, R₃, R_FiveAnd R
₆Is a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or
Represents an acylamino group, R ₃Is R₂With nitrogen-containing 5
Even if it represents a non-metallic atomic group forming a six-membered ring
Good. Y₁, Y₂Is a hydrogen atom or an oxidant of the developing agent
Represents a group capable of splitting off during the coupling reaction of. n is 0 or
Represents 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-
Examples thereof include a butyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-II) are as follows. Preferred R ₁ in the general formula (CI) is an aryl group or a heterocyclic group, and a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, An aryl group substituted with a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group is more preferable.

In the general formula (CI), when R ₃ and R ₂ do not form a ring, R ₂ is preferably a substituted or unsubstituted alkyl group or an aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. R ₃ is preferably a hydrogen atom. In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. Preferred R in the general formula (C-II)
₅ is a methyl group having an alkyl group having 2 to 15 carbon atoms and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group or an alkyloxy group.

In the general formula (C-II), R ₅ has 2 to 2 carbon atoms.
More preferably, it is an alkyl group having 15 carbon atoms.
Particularly preferably, it is an alkyl group of 4 to 4. Preferred R ₆ in the general formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. In formulas (C-I) and (C-II), preferred Y ₁ and Y ₂ are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group, respectively.

In the general formula (M-1), R ₁ and R
₉ represents an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents a hydrogen atom or a leaving group. R ₇
And the permissible substituents of the aryl group (preferably phenyl group) of R ₉ are the same as the permissible substituents of the substituent R ₁ , and when two or more substituents are present, they may be the same or different. May be. R ₈ is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferred Y ₃ is of the type that leaves at either a sulfur, oxygen or nitrogen atom, such as US Pat. No. 4,351,897 and International Publication WO88 / 04.
Particularly preferred are the sulfur atom-dissociated types, such as those described in US Pat.

In formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferable.
Za, Zb and Zc represent methine, substituted methine, = N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. Zb
When the -Zc bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or higher multimer, Za, Zb or Z
When c is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is included.

Among the pyrazoloazole type couplers represented by the general formula (M-II), the imidazo [1,2- b] pyrazoles are preferred, and pyrazolo [1,5 are described in US Pat. No. 4,540,654.
Particularly preferred is -b] [1,2,4] triazole. In addition, a branched alkyl group as described in JP-A-61-65245 has a pyrazolotriazole ring of 2, 3 or 6.
Pyrazolotriazole coupler directly connected to the position
Pyrazoloazole couplers containing a sulfonamide group in the molecule, as described in JP-A 1-65246, Japanese Patent Laid-Open No.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in 1-147254 and European Patent (Publication) Nos. 226,849 and 294,78.
It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 5.

In the general formula (Y), R₁₁Is a halogen source
Child, alkoxy group, trifluoromethyl group or aryl
Represents a radical, R₁₂Is a hydrogen atom, a halogen atom or
Represents a koxy group. A is -NHCOR₁₃, -NHSO₂-R₁₃,-
SO₂NHR₁₃, -COOR₁₃, -SO₃N (R₁₄) R₁₃Represents However,
R₁₃And R₁₄Is an alkyl group, aryl group or
Represents a sil group. Y_FiveRepresents a leaving group. R₁₂And R₁₃, R₁₄
The substituent of R is R ₁Same as the permissible substituents for
Same as the leaving group Y_FiveIs preferably an oxygen atom or nitrogen
Nitrogen atom
The detachable type is particularly preferable.

The couplers represented by the above general formulas (CI) to (Y) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol per mol of silver halide. , Preferably 0.1 to 0.5 mol. In the present invention,
Various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by the so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion.

As a dispersion medium for such a coupler, a high boiling point organic solvent having a dielectric constant (25 ° C.) of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound is used. Preferably. As the high boiling point organic solvent, preferably used are high boiling point organic solvents represented by the following general formulas (A) to (E). In particular, the above general formulas (C-I) and (C
-II), (M-1), (M-II) and (Y) are particularly preferred.

General formula (A)

[0071]

[Chemical 4]

General formula (B) W ₁ -COO-W ₂ General formula (C) W ₁ -CON-W ₂ (W ₃ ) General formula (D)

[0073]

[Chemical 5]

General formula (E) W₁-OW₂ (W in the formula₁, W₂And W₃Are replaced or nothing
Substituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W_FourIs W ₁, OW
₁Or SW₁And n is an integer of 1 to 5
Yes, W when n is 2 or more_FourAre the same or different
In general formula (E), W ₁And W₂Is condensed
May form a ring).

The high-boiling organic solvent which can be used in the present invention is a compound which is immiscible with water and has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, other than those represented by the general formulas (A) to (E). If it can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher, more preferably 1
It is 70 ° C or higher.

Details of these high boiling point organic solvents are described in JP-A-62-215272, No. 137.
It is described in the lower right column of the page to the upper right column of page 144. Further, these couplers are impregnated with a loadable latex polymer (for example, U.S. Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution. The homopolymers or copolymers described on pages 12 to 30 of WO88 / 00723 are preferably used, and the use of an acrylamide polymer is particularly preferable in terms of color image stabilization and the like.

The light-sensitive material produced by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as an antifoggant. Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as an organic anti-fading agent for cyan, magenta and / or yellow images, hydroquinones, 6-hydroxychromans, 5-
Hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenols and other hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and phenolic hydroxyl groups of these compounds Typical examples are silylated and alkylated ether or ester derivatives. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents. Hydroquinones are US patents
2,360,290, 2,418,613, 2,700,453,
No. 2,701,197, No. 2,728,659, No. 2,732,300
No. 2,735,765, No. 3,982,944, No. 4,430,
425, British Patent 1,363,921, U.S. Patent 2,710,80
Nos. 1, 2,816,028 and 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are described in U.S. Pat. Nos. 3,432,300, 3,573,050, and 3,57.
4,627, 3,698,909, 3,764,337, and JP-A-52-152225. Spiroindanes are described in U.S. Pat. ,
Hindered phenols are disclosed in U.S. Pat. No. 3,700,45 in JP-A-59-10539 and JP-B-57-19765.
5, JP-A-52-72224, U.S. Pat. No. 4,228,23
5, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in US Pat. Nos. 3,457,079 and 4,332,886, respectively.
And Japanese Patent Publication No. 56-21114, the hindered amines include U.S. Pat. Nos. 3,336,135, 4,268,593, British Patents 1,326,889, 1,354,313, 1,410,
No. 846, Japanese Patent Publication No. 51-1420, JP-A No. 58-114
No. 036, No. 59-53846, No. 59-783.
No. 44, etc., metal complexes are described in US Pat. Nos. 4,050,938, 4,241,155, British Patent 2,027,731 (A), etc., respectively. These compounds are usually contained in an amount of 5 to 100% by weight based on the corresponding color coupler.
By co-emulsifying with a coupler and adding to the photosensitive layer,
The purpose can be achieved. In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (see, for example, US Pat.
533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, JP-A-4)
6-2784), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,395), butadiene compounds (US Pat. No. 4,045,
229) or a benzoxoxide compound (eg, US Pat. Nos. 3,406,070 and 3,677,672).
And those described in No. 4,271,307). An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorbers may be mordanted in a specific layer.

Of these, the benzotriazole compounds substituted with the aryl group are preferable. Further, it is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of color dyes by the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

The preferred compound (F) is p-
Second-order reaction rate constant k with anisidine ₂(80 ℃ trio
(In octyl phosphate) 1.0 liter / mol ・ sec 〜
1 x 10^-FiveCompounds that react in the range of liter / mol-sec
It is a thing. The second-order reaction rate constant is described in JP-A-63-15.
It can be measured by the method described in No. 8545. k₂
Is larger than this range, the compound itself is unstable.
May react with gelatin or water and decompose.
It On the other hand, k₂Is smaller than this range, residual aroma
Slow reaction with group amine developing agents, resulting in residual
Can prevent the side effects of aromatic amine developing agents
Sometimes there is not.

More preferable compounds (F) can be represented by the following general formula (FI) or (FII). Formula _{(FI) R 1 - (A} ) n -X Formula _{(FII) R 2 -C (B} ) = Y in formula, R _1, R ₂ each represents an aliphatic group, an aromatic group or a heterocyclic group, Represents n represents 1 or 0. A represents a group which reacts with an aromatic amine-based developing agent to form a chemical bond, and X represents a group which reacts and leaves as an aromatic amine-based developing agent. B is a hydrogen atom, an aliphatic group, an aromatic group,
Represents a heterocyclic group, an acyl group, or a sulfonyl group, and Y
Represents a group that promotes addition of the aromatic amine-based developing agent to the compound of formula (FII). Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with the residual aromatic amine-based developing agent, representative ones are substitution reaction and addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545,
No. 62-283338, European Patent Publication 298321.
Nos. 277,589 and the like are preferred. On the other hand, a more preferred compound (G) which chemically bonds with an oxidized product of an aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and colorless compound is represented by the following general formula (GI) ).

General formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilic ⁿ CH ₃ I value (RG Pear
son. et al., J. Am. Chem. Soc., 90 , 319 (19)
68)) is preferably a group of 5 or more, or a group derived therefrom.

Specific examples of the compound represented by the general formula (GI) are described in European Patent Publication No. 255722 and JP-A-62-1.
No. 43048, No. 62-229145, and Japanese Patent Application No. 63-
Those described in No. 136724, No. 62-214681, European Patent Publication No. 298321, No. 277589 and the like are preferable. Further, for details of the combination of the compound (G) and the compound (F), European Patent Publication 277 is disclosed.
589.

The light-sensitive material produced according to the present invention contains a hydrophilic colloid or a dye which becomes water-soluble by photographic processing for various purposes such as a filter dye in a hydrophilic colloid layer, prevention of irradiation or halation, and the like. It may be contained. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, gelatin may be either lime-treated or acid-treated. See Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic
Press, issued in 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrace film, polyethylene terephthalate or the like which is generally used in a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of printing materials having a reflective support is more preferred. The "reflective support" used in the present invention means one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, and the like.

As the other reflection type support, a support having a specular reflection or type II diffuse reflection metal surface can be used. The metal surface preferably has a spectral reflectance in the visible wavelength range of 0.5 or more, and the metal surface is preferably roughened or made to be diffuse reflective by using a metal powder. As the metal, aluminum, tin, silver, magnesium, or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, or plating. Among them, it is preferable to obtain the metal by vapor-depositing a metal on another substrate. It is preferable to provide a water resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the support side of the support of the present invention having the metal surface.
For the details of such a support, see, for example, JP-A-6-6
1-210346, 63-24247, 63-
No. 24251 and No. 63-24255. These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use a pigment particle whose surface is treated with a dihydric or tetrahydric alcohol. The occupying area ratio (%) per defined unit area of the white pigment fine particles is most typically the observed area is divided into contiguous unit areas of 6 μm × 6 μm,
Occupied area ratio (%) of fine particles projected on the unit area
(R _i ) can be measured and obtained. The variation coefficient of the occupied area ratio (%) is R _i with respect to the average value (R) of R _i.
Can be obtained by the ratio s / R of the standard deviation s of.
The number (n) of the target unit areas is preferably 6 or more.
Therefore, the coefficient of variation s / R is

[0091]

[Equation 1]

It can be obtained by In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is
0.15 or less, particularly 0.12 or less is preferable. When it is 0.08 or less, it can be said that the dispersibility of the particles is substantially “uniform”.

[0093]

EXAMPLES Examples of the present invention will be specifically shown below, but the present invention is not limited thereto. Example 1 Fuji Color Paper Super FA Type II (manufactured by Fuji Photo Film Co., Ltd.) was imagewise exposed and then continuously processed in the following processing steps. A processor of Fuji Color Paper Processor FPRP409 (manufactured by Fuji Photo Film Co., Ltd.) was partially modified and used. Linear speed 9 m / min Leader belt transport system With two leader belts, up to 4 rows of paper can be processed at the same time. 1st row 20% 2nd row 30% 3rd row 40% 4th row 10%

Treatment Process Process Temperature Time Replenishment Amount Tank Capacity ℃ sec ml / m ² liter Color Development 39 45 60 500 Bleach Fix 30-35 45 55 500 Rinse 30-35 20 ---- 200 Rinse 30-35 20- --200 Rinse 30 to 35 20 ---- 200 Rinse 30 to 3520 20 ---- 200 Rinse 30 to 35 20 300 200 (Rinse is a countercurrent system of →→→→. New tank liquid for developer. The tank has a capacity of 100 liters.)

The above printing material 17,000 m ² (width 8.9c
m) was continuously treated by the following three methods over 10 days. In this method, the average carryover amount was 57 ml / m ² . That is, each processing tank was filled with the tank liquid at the start of the continuous processing. After processing starts
The replenisher was replenished every 10 m ² of processed area of the light-sensitive material. The leader belt did not stop at all during the processing period of 10 days, but the total time for processing the light-sensitive material in the processing tank was 16 hours per day. Test 1 (conventional): Simply replenish test 2 (comparison): Liquid surface of color developing tank is overflow hole (located 10 cm from the top of the tank)
When it drops from 2 cm (corresponding to about 10 liters),
Add water and correct to the standard liquid level (down to the overflow hole). Test 3 (Invention): The liquid surface of the color developing tank is an overflow hole (located 10 cm from the upper surface of the tank).
When it drops from 2 cm (corresponding to about 10 liters),
Add new liquid (tank liquid) and correct to the standard liquid level (up to the bottom of the overflow hole). The treatment solutions used are as follows.

Color developer New tank solution Replenisher Triethanolamine 10g 10g 1-Hydroxyethylidene 1,1-diphosphonic acid (60wt%) 2g 2g Diethylenetriaminepentaacetic acid 1g 1g Nitrilo-N, N, N-trimethylenephosphonic acid ( 40wt%) 8g 8g potassium chloride 6.5g ---- potassium bromide 0.02g ---- hydrazinodiacetic acid 5g 9g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulfate 5g 13g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical) 1.25g 3.5g Potassium carbonate 25g 25g Sodium sulfite 0.1g ---- Add water 1000ml 1000ml KOH pH 10.00 11 .10

Bleach-fixing solution New tank solution replenishing solution Ammonium thiosulfate (70 W / V%) 110 ml 220 ml Ammonium sulfite monohydrate 19.4 g 38.8 g EDTA 1.5 g 3.0 g EDTA FeNH ₄ 55 g 110 g Ammonium bromide 25 g 50 g Nitrate (67%) 24.5g 49g Add water 1000ml 1000ml pH 5.20 4.80 Rinse solution Ion-exchanged water (3ppm each for calcium and magnesium)
In the following tests 1 to 3, in order to evaluate daily changes in photographic characteristics, Fuji Color Paper Control Strips Super FA TYPE II (manufactured by Fuji Photo Film Co., Ltd.) was processed every day from the start point. Changes in processing characteristics (changes in sensitivity LD and gradation C) were obtained. The change values of magenta density are shown in Table 1. For example, +5 is density 0.
05 indicates an increase, -value indicates a decrease in concentration. The results are shown in Table 1.

[0098]                               Table 1     ─────────────────────────────                   Test 1 Test 2 Test 3 *       Experiment day ───────────────────────                   LD C LD C LD C     ─────────────────────────────       Day 1 0 0 0 0 0 0 0       2 -3 +2 -2 -2 -1 +1       3-5 +4 -4 -3 -1 +1       4-7 +6 -6 -5 -1 +2       5-10 +7 -7 -7 -2 +2       6-12 +8 -8 -8 -2 +2       7 -14 +9 -9 -9 -2 +2       8-16 +10 -10 -10 -2 +3       9-17 +11 -11 -10 -3 +3       10 -18 +11 -11 -10 -3 +3     ─────────────────────────────       * The present invention

In Test 1, the liquid surface gradually decreased, and after 5 days, a decrease of about 50 L occurred, and air was introduced into the circulation system to oxidize the developer. In addition, the processing time is shortened as the liquid level is lowered, and the sensitivity is significantly reduced as the liquid is concentrated, and the contrast is high. In Test 2, the running fluid (working
Due to the dilution of (solution), sensitivity deterioration and softening gradually occur, which is not preferable photographic characteristics. In Test 3 (invention), good results were obtained with almost no change in photographic characteristics.

Example 2 A multi-layer color photographic paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows. First layer coating liquid preparation Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-7) 0.
7 g of ethyl acetate 27.2 cc and solvent (Solv-1)
8.2 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.82 μm, grain size distribution variation coefficient 0.08, silver bromide 0.2 mol% is locally contained on the grain surface)
The blue-sensitive sensitizing dyes shown below are added in an amount of 2.0 × 1 per mol of silver.
A sulfur-sensitized product was prepared by adding 0 ^-4 mol.
The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively, in an amount of 8.5 × 10 ^-5 mol / mol of silver halide. 0.7 x 10 ^-4
Mol, 2.5 × 10 ⁻⁴ mol.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added at 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. The following dyes were added to the emulsion layer to prevent irradiation.

[0103]

[Chemical 6]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains titanium oxide and bluing dye (ultraviolet)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.25 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixture Inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

[0105] Third layer (green feeling layer)   Silver chlorobromide emulsion (cube, average grain size 0.40 μm), variation of grain size distribution The coefficient was 0.08, and 0.8 mol% AgBr was locally contained on the particle surface.)                                                 0.12   Gelatin 1.24   Magenta coupler (BxM) 0.20   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-3) 0.15   Color image stabilizer (Cpd-4) 0.02   Color image stabilizer (Cpd-9) 0.02   Solvent (Solv-2) 0.40 Fourth layer (UV absorption layer)   Gelatin 1.58   UV absorber (UV-1) 0.47   Color mixing inhibitor (Cpd-5) 0.05   Solvent (Solv-5) 0.24

[0106] Fifth layer (red sensitive layer)   Silver chlorobromide emulsion (cube, average grain size 0.60 μm, variation factor of grain size distribution) The number is 0.09, and AgBr 0.6 mol% was locally contained in a part of the particle surface.)                                                 0.20   Gelatin 1.34   Cyan coupler (BxC) 0.32   Color image stabilizer (Cpd-6) 0.17   Color image stabilizer (Cpd-7) 0.40   Color image stabilizer (Cpd-8) 0.04   Solvent (Solv-6) 0.15 Sixth layer (UV absorption layer)   Gelatin 0.53   Ultraviolet absorber (UV-1) 0.16   Color mixing inhibitor (Cpd-5) 0.02   Solvent (Solv-5) 0.08 Seventh layer (protective layer)   Gelatin 1.33   Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%)                                                 0.17   Liquid paraffin 0.03

[0107]

[Chemical 7]

[0108]

[Chemical 8]

[0109]

[Chemical 9]

[0110]

[Chemical 10]

[0111]

[Chemical 11]

[0112]

[Chemical 12]

[0113]

[Chemical 13]

The following were used as the spectral sensitizing dye for each layer. Blue-sensitive emulsion layer

[0115]

[Chemical 14]

(Each mole of silver halide is 2.0 × 10 ^-4 mole for large size emulsion and 2.5 × 10 ^-4 mole for small size emulsion) Green-sensitive emulsion layer

[0117]

[Chemical 15]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, and for small size emulsion)
5.6 × 10 ^-4 mol) and

[0119]

[Chemical 16]

(7.0 × 10 ^-5 mol for large size emulsion and 1.0 × 10 ^-5 mol for small size emulsion per mol of silver halide) Red-sensitive emulsion layer

[0121]

[Chemical 17]

(Per mol of silver halide, 0.9 × 10 ⁻⁴ mol for large size emulsion, and 1.1 × 10 ⁻⁴ mol for small size emulsion) For red-sensitive emulsion layer The following compounds were added in an amount of 2.6 × 10 ⁻⁴ mol per mol of silver halide.

[0123]

[Chemical 18]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol, 2.5 per mol
× 10 ^{−5 was} added. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. The following dyes were added to the emulsion layer to prevent irradiation.

[0125]

[Chemical 19]

The sample obtained as described above was used as Sample II-
It was set to 1. Next, Samples II-2 to 5 were prepared by changing the silver halide composition of each emulsion layer as follows. Sample No. Blue-sensitive layer Green-sensitive layer Red-sensitive layer II-1 99.8 99.2 99.4 II-2 95.7 95.1 95.3 II-3 90.1 90.3 90.3 II- 4 85.1 85.5 85.4 II-5 79.8 80.1 80.2 (Numerical values represent silver chloride content in silver chlorobromide emulsion in mol%)

As the processor, Fuji Color Paper Processor FPRP202L (manufactured by Fuji Photo Film Co., Ltd.) was partially modified and used.・ Linear velocity 2m / min ・ Leader belt transport system Up to 4 rows of paper can be processed simultaneously with two leader belts. The processing steps are as follows. Using this processor, Sample II-1 which was imagewise exposed in the following processing steps was continuously processed.

Treatment Step Temperature Time Replenishment Amount Tank Capacity ° C sec ml / m ² liter Color Development 39.0 45 55 50 Bleach Fix 30-35 45 55 50 Rinse 30-35 20 ----- 20 Rinse 30-35 20 150 20 Washing with water 30-35 20 ----- 20 Washing with water 30-35 20 ----- 20 Washing with water 30-35 20 4000 20 (Rinse was → washing with →→ countercurrent method)

The above printing material (1900 m ² ) was continuously treated for 10 days by the following two methods. Here, the new tank solution and the replenisher solution were properly used as in Example 1. Test 4 (Comparison): If the liquid level in the color development tank drops, add water to correct the liquid level. Test 5 (Invention): When the level of the color developing solution tank drops, a new solution (tank solution) is added to correct the level. The treatment liquids used are as follows.

Color developer New tank solution Replenisher Triethanolamine 10g 10g Ethylenediaminetetraacetic acid 3g 3g Catechol-3,5-disulfonic acid 0.3g 0.3g N, N-di (phosphonoethyl) hydroxylamine 5.0g 10. 0 g Potassium chloride 6.7 g ---- Potassium bromide 0.03 g ---- N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5 g 13 g Fluorescence enhancement Whitening agent (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.25 g 3.0 g Potassium carbonate 25 g 25 g Water was added to 1000 ml 1000 ml pH 10.00 11.20 (pH adjusted with KOH.) The same solution was used. Further, tap water was used as the rinse liquid and the washing water. In the above Tests 4 and 5, in order to evaluate daily changes in photographic characteristics, samples II-1 to 5 were exposed to light through a wedge wedge and processed once every two days. The change in the photographic characteristics of The change in photographic characteristics is indicated by the amount of change in density at the exposure point where the density is 1.0 at the start. The amount of change in cyan density is shown in Table 2.

[0131]                             Table 2 ───────────────────────────────────                                   Test date (days)     Treatment Sample ───────────────────────                         0 2 4 6 8 10 ───────────────────────────────────   Test 4 II-1 0 -2-5 -8 -10 -11               II-20 -5 -8 -10 -11               II-30-2-5-5-8-10-12               II-40-0-6-8-8-11-12               II-5 0 -2-6 -9 -11 -12 ───────────────────────────────────   Test 5 II-1 0 0 0 -1 -1 -1               II-2 0 0 0 -1 -1 -1               II-3 0 0 -1 -2 -2 -2   Present Invention II-40-2-3-4-5-5-5               II-5 0-2 -3 -4 -5 -5 ───────────────────────────────────

According to the processing method of the present invention, the photographic characteristics during continuous processing are very stable. Especially, in Samples II-1, 2 and 3 using the high silver chloride emulsion, the effect is remarkable.

Example 3 A multilayer color photographic paper having the following layer constitution was prepared on a paper support which was laminated on both sides with polyethylene and whose surface was subjected to corona discharge treatment. The coating solution was prepared as follows. First layer coating liquid preparation Yellow coupler (ExY) 60.0 g and anti-fading agent (Cpd-1) 28.0 g Ethyl acetate 150 cc and solvent (Solv-3) 1.0 cc and solvent (Solv-4) 3.0 cc
Was added and dissolved, and this solution was added to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then dispersed by an ultrasonic homogenizer, and the obtained dispersion was a salt containing the following blue-sensitizing dye. A first layer coating solution was prepared by mixing and dissolving it in 420 g of a silver bromide emulsion (0.7 mol% of silver bromide).

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-Bis (vinylsulfonyl) ethane was used as the gelatin hardening agent for each layer. The following were used as the spectral sensitizing dyes for each layer. Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,
3'-Disulfoethylthiacyanine hydroxide green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3 ' -Diethyl-5-methoxy-
9,11-Neopentyl thiadicarbocyanine iodide

A 7: 2: 1 mixture (molar ratio) of the following three components was used as a stabilizer for each emulsion layer. 1- (2-acetoaminophenyl) -5-mercaptotetrazole 1-phenyl-5-mercaptotetrazole 1- (p-methoxyphenyl) -5-mercaptotetrazole The following were used as anti-irradiation dyes. [3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N ′-(4,8-Dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy -4- (3- (3-cyano-5-oxo-1- (4-sulfonatophenyl) -2
-Pyrazolin-4-ylidene) -1-benzanyl) -1
-Pyrazolyl] benzene-4-sulfonate-sodium salt

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Paper support first layer laminated on both sides with polyethylene support and corona discharge treated (blue sensitive layer) Silver chlorobromide emulsion (ArBr 0.7 mol%, cubic, average grain size 0.9 μm) 0.30 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (Color mixing inhibitor) Gelatin 0.80 Anti-Color Mixing Agent (Cpd-2) 0.055 Solvent (Solv-1) 0.03 Solvent (Solv-2) 0.015 Third Layer (Green Sensitive Layer) Silver Chlorobromide Emulsion (ArBr 0.7) Mol%, cubic, average particle size 0.45 μm) 0.20 Gelatin 1.86 Magenta coupler (ExM) 0.27 Anti-fading agent (Cpd-3) 0.17 Anti-fading agent (Cpd-4) 0.10 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.03

[0137] Fourth layer (color mixing inhibitor)   Gelatin 1.70   Color mixing inhibitor (Cpd-2) 0.065   UV absorber (UV-1) 0.45   Ultraviolet absorber (UV-2) 0.23   Solvent (Solv-1) 0.05   Solvent (Solv-2) 0.05 Fifth layer (red sensitive layer)   The above-mentioned silver chlorobromide emulsion (ArBr 0.4 mol%, cubic, average grain size 0.5 μm)                                                           0.20   Gelatin 1.80   Cyan coupler (ExC-1) 0.26   Cyan coupler (ExC-2) 0.12   Anti-fading agent (Cpd-1) 0.20   Solvent (Solv-1) 0.16   Solvent (Solv-2) 0.09   Coloring accelerator (Cpd-5) 0.15

[0138] Sixth layer (UV absorption layer)   Gelatin 0.70   Ultraviolet absorber (UV-1) 0.26   Ultraviolet absorber (UV-2) 0.07   Solvent (Solv-1) 0.30   Solvent (Solv-2) 0.09 Seventh layer (protective layer)   Gelatin 1.07 (Cpd-1) anti-fading agent

[0139]

[Chemical 20]

(Cpd-2) Anti-color mixing agent 2,5-di-tert-octylhydroquinone (Cpd-3) Anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2 , 2'-Spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color development accelerator p- (p-toluenesulfonamide) phenyl-dodecane (Solv-1) solvent Di (2-ethylhexyl) phthalate (Solv-2) solvent Dibutyl phthalate (Solv-3) solvent Di (i-nonyl 9) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-
Di-t-amylbenzene

(UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-) Di-tert-butylphenyl) benzotriazole

[0142]

[Chemical 21]

[0143]

[Chemical formula 22]

The sample thus obtained was used as Sample IIIA.
Furthermore, samples III B, III C, III D and III E were prepared by changing the coating silver amount of each layer as shown in the table below. ──────────────────────────── coated silver amount (g / m ²⁾ ───────────── ───────── Sample 1st layer 3rd layer 5th layer Total ──────────────────────────── III A 0.30 0.20 0.20 0.70 III B 0.32 0.22 0.21 0.75 III C 0.35 0.22 0.23 0.80 III D 0.35 0.24 0.2. 26 0.85 III E 0.37 0.25 0.30 0.92 ─────────────────────────────

Sample IIIA imagewise exposed was continuously processed in the same processing steps as in Example 2. Sample III A
Imagewise exposure of 2000 m ² each was followed by continuous treatment for 20 days by the following two methods. Test 6 (Comparison): If the liquid level in the color developing tank drops, add water to correct the liquid level. Test 7 (Invention): When the liquid level in the color developing tank is lowered, a new liquid (new tank liquid) is added to correct the liquid level. The composition of each treatment liquid is as follows.

Color developer New tank solution Replenisher Triethanolamine 10 g 10 g 1-Hydroxyethylidene 1,1-disulfonic acid (60%) 2 g 2 g Lithium sulfate 1 g 1 g Potassium chloride 5.7 g ---- Potassium bromide 03 g ---- N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g 12 g Optical brightener (UVITEX CK manufactured by Ciba Geigy) 1.0 g 2 0.0 g Potassium carbonate 25 g 25 g Water was added to 1000 ml 1000 ml KOH pH 10.00 11.20 The bleach-fix solution, rinse solution and washing with water were the same as in Example 2.

In Tests 6 and 7 above, in order to evaluate daily changes in photographic characteristics, the samples III A, B, C, and
Samples exposed through wedge wedges of D and E were processed once every two days to determine the change in photographic properties from the start. Changes in photographic characteristics are density at the start
The density change amount at the exposure point showing 1.0 is shown. The amount of change in magenta density is shown in Table 3.

Table 3 ────────────────────────────────── Test day (days) Treatment sample ──── ─────────────────── 0 2 4 6 8 10 ────────────────────────── ───────── Test 6 III A 0 -4-6 -9 -11 -12 III B 0 -4 -6 -9 -11 -12 III C 0 -4 -7 -10 -11 -12 III D 0 -4-7 -10 -12 -13 III E 0 -5 -7 -10 -12 -13 ───────────────────────── ────────── Test 7 III A 0 0 0 +1 +1 +1 III B 0 +1 +2 +2 +2 III C 0 0 +2 +3 +3 +3 Present invention III D 0 +1 +3 +4 +6 +6 III E 0 +2 +3 +4 +6 +6 ──────────────── ───────────────── In the present invention, the sensitivity change is small, especially coated silver amount 0.
The effect is remarkable in the samples III A, III B, and III C that weigh less than 8 g.

[0149]

By using the method of the present invention, stable photographic characteristics can be maintained even if the amount of processing liquid waste is greatly reduced or eliminated. In particular, it is effective for the stability of processing of a high silver chloride color light-sensitive material.

Claims (3)

[Claims] 1. In a processing method of continuously processing an imagewise exposed silver halide photographic light-sensitive material while replenishing a replenisher, a new solution (new tank solution) ) Is added to the silver halide photographic light-sensitive material. 2. The processing method according to claim 1, wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material containing a high silver chloride emulsion, and the processing liquid is a color developing solution. 3. The processing method according to claim 2, wherein the replenishing amount of the replenishing liquid is equal to or less than the average carryover amount (average carry-out amount).