JP3047278B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to a method in which the processing solution has good low-temperature aging properties and does not cause an increase in stain even when the replenishing amount is reduced. The present invention relates to a processing method capable of quick desilvering.

[0002]

2. Description of the Related Art In recent years, in the processing of silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), short-time processing and response to environmental problems have become the most important issues. The former is due to the demand for processing films and prints in the shortest possible time to differentiate itself from other stores due to the spread of small in-store processing labs called mini labs. was there. In the latter case, environmental pollution at the global level has been highlighted, and strict regulations have been made on emissions into the environment every year. Therefore, in the photographic industry, reduction of photographic waste liquid has become a major issue. Processing of the photosensitive material is generally performed using a processor called an automatic developing machine. This automatic processor has processing tanks for color development, bleaching, bleach-fixing, fixing, washing, etc., and performs processing by passing photosensitive materials such as color films and color papers sequentially through these processing tanks. is there. Each processing tank is replenished with a processing liquid called a replenisher in accordance with the area of the photosensitive material to be processed in order to keep the performance of the processing liquid constant. At this time, the processing liquid overflowing from the processing tank is discharged as photographic waste liquid as it is It is generally done.

[0003] Short-time processing (rapid processing) and reduction of waste liquid (ie, reduction of replenishment amount) have been studied for each processing step. For example, in the case of a solution having bleaching ability (bleach solution or bleach-fix solution), in order to speed up and reduce replenishment,
It is important to keep the bleach and other processing components at a somewhat high concentration. Further, the bleaching solution in the processing tank in the automatic developing machine is brought into a state in which the concentration of the bleaching agent in the replenisher is diluted due to the carry-in of the prebath processing solution by the photosensitive material.
Therefore, the replenisher is set to a high concentration in advance in consideration of this dilution, but as the replenishment amount is reduced, the concentration difference between the replenisher and the bleaching agent in the processing tank becomes larger, so that the replenisher is rapidly and lowly concentrated. When performing the replenishment process, a very high concentration replenisher must be supplied. This replenishing solution processing agent is supplied from a processing agent manufacturer in a normal laboratory (development laboratory). As a supply method, a "use liquid supply" in which the processing agent is supplied in a form that can be used as it is, Either of "concentration kit supply", in which the treating agent is supplied as a concentrated liquid or solid and prepared by adding water at the time of use, is generally used. However, in the case of a solid concentration kit such as a powder or a solid, since dissolution generally takes a long time, it is preferable to supply a working solution that can be used as it is as a replenisher from the viewpoint of simplicity of preparation. . In any case, a high-concentration treating agent is required when supplying a liquid preparation that is low in replenishment and easy to prepare, and in this case, problems such as precipitation occur even when stored at low temperature because of high solubility at low temperature. A treatment agent that does not generate is desired.

As a quick bleaching agent, a ferric salt such as ferric chloride or a combination thereof with an organic acid such as citric acid (for example, JP-A-58-116538) is known as a strong oxidizing agent. However, it is hardly used in recent years because of its strong corrosiveness to metals and strong irritation to human skin. Bichromates and red blood salts are also known as rapid bleaching agents, but are rarely used because of their adverse environmental effects when discharged. In recent years, aminopolycarboxylic acid ferric complex-based bleaching agents such as ethylenediaminetetraacetic acid ferric complex have been widely used as bleaching agents having relatively little adverse effect on the environment. It is known that the pH of a solution having bleaching ability is lowered to 5.5 or less as a means for enhancing the desilvering property of the ferric ethylenediaminetetraacetic acid complex salt. It is known to use Among the aminopolycarboxylic acid ferric complex salts, a bleaching agent capable of rapid bleaching is disclosed in JP-A-62-222.
No. 252 describes a ferric complex of 1,3-diaminopropanetetraacetic acid. Such a high potential and strong oxidizing power aminopolycarboxylic acid ferric complex salt bleach is effective in rapidity, but has a bleaching ability for the purpose of preventing bleaching fog generated due to its strong oxidizing power. PH of the liquid having
To a low pH of 5.5 or less, and a buffer such as acetic acid to bring the pH into the low pH range is required. This acetic acid has been conventionally used in a solution having a bleaching ability of an aminopolycarboxylic acid ferric complex salt because it is preferable in terms of performance such as prevention of bleaching fog and no adverse effect on desilvering. Then, since the odor is strong, it is difficult to use in a laboratory, and an odorless buffer instead of acetic acid has been desired.

For example, Japanese Patent Application Laid-Open No. 3-188443 discloses that
A treatment method using a polybasic acid such as malonic acid, fumaric acid or succinic acid as an acetic acid substitute has been proposed. Some of these polybasic acids are odorless and prevent bleaching fog. However, the processing solution (particularly, replenisher) has poor crystallization at low temperature, which is a practical problem. Also, Japanese Patent Application Laid-Open No. Hei 3-1505
No. 63 proposes the addition of a monobasic carboxylic acid having a non-dissociable hydrophilic substituent such as glycolic acid or lactic acid. However, although these acids are also preferable in terms of odor, a large amount of addition is required to prevent bleaching fog,
In this case, the desilvering property is deteriorated, so that it is not suitable for rapid processing. It is necessary to use acetic acid in combination, and it is difficult to achieve both odor and rapid desilvering. Also, when the bleaching solution is run at a low replenishment rate, the concentration of the color developing solution brought into the bleaching solution by the light-sensitive material increases, and the unexposed areas such as color films and color papers are caused by this. It was found that the increase in the density, that is, the stain level, was worsened, which was a problem along with the bleaching fog and the low-temperature precipitation property described above.

[0006]

Therefore, even if a treating agent in which a bleaching agent is dissolved in a high concentration is stored at a low temperature, precipitation does not occur, and a treating solution having a bleaching ability is treated with a low replenishment. Also, a processing agent which has a quick desilvering and generates less stain such as bleaching fog has been desired. The present invention solves the above problems.

[0007]

The inventor of the present invention has conducted various studies on the above problems, and has achieved the following processing method. That is, in a method of processing a silver halide color photographic light-sensitive material with a solution having a bleaching ability, the solution having the bleaching ability contains a ferric aminopolycarboxylic acid complex salt as a bleaching agent and has a pH of 2 or less.
And 5.5 or more, and further comprises two or three of succinic acid, glutaric acid and adipic acid. In particular, in the above-mentioned processing method, the liquid having bleaching ability contains all three types of succinic acid, glutaric acid and adipic acid, and the liquid having bleaching ability is a liquid 1 having bleaching ability for nitric acid compounds. The present invention is that the bleaching solution has a concentration of 0 to 0.3 mol (including 0) per liter, and the solution having a bleaching ability is a bleaching solution, and the solution having a subsequent fixing ability contains an imidazole compound. Has been found to be favorable for the achievement of Advantageous Effects of Invention According to the present invention, even when a liquid processing agent having bleaching ability is stored at a low temperature, precipitation does not occur, and good performance in which stain is not generated even when processing is performed with low replenishment using this processing agent. Is obtained.

Hereinafter, the present invention will be described in more detail. In the present invention, the bleaching liquid contains two or three of succinic acid, glutaric acid and adipic acid. The addition amount of these organic acids is preferably 0.02 to 1.5 mol, more preferably 0.03 to 1.2 mol, per liter of a liquid having bleaching ability. As a more preferred range for each, succinic acid is used in an amount of 0.03 to 0.8 mol per liter of a liquid having a bleaching ability, and particularly preferably 0.1 to 0.7 mol. Glutaric acid is used in an amount of from 0.03 to 1.1 mol per liter of a solution having a bleaching ability, and from 0.3 to 1.
0 mol is particularly preferred. Adipic acid is used in an amount of 0.03 to 0.18 mol per liter of a liquid having a bleaching ability, and 0.1 to 0.1 mol.
04 to 0.10 mol is particularly preferred. If the amount of each addition is small, the effect of the present invention is significantly reduced, and if it is too large, the solubility at low temperatures is deteriorated. The total of these organic acids is preferably from 0.3 to 2.5 mol per liter of a liquid having bleaching ability, and more preferably from 0.5 to 1.
Two moles are preferred. Of these, it is preferable to include at least adipic acid, and then it is preferable to include at least succinic acid. More preferably, it contains both adipic acid and succinic acid, and most preferably, it contains all three of succinic acid, glutaric acid and adipic acid. The replenisher of the solution having the bleaching ability includes 1.1 to 3 of the solution having the bleaching ability.
It contains twice the above organic acid but the smaller the replenishment amount,
This ratio will be higher. PH of the solution having bleaching ability of the present invention
Is 2.0 to 5.5, preferably 3.5 to 5.5,
More preferably, it is 4.0 to 5.0. Further, the pH of the replenisher of the solution having the bleaching ability is 2.0 to 5.0, preferably 3.0 to 5.0, and more preferably 3.5 to 4.5. If the pH is too low, the solubility of the bleach at low temperatures will decrease, causing precipitation. On the other hand, if it is too high, the bleaching speed decreases, and rapid desilvering becomes impossible.

The bleaching solution of the present invention is a bleaching solution or a bleach-fixing solution. Generally, the desilvering process of the photosensitive material
It is composed of a bleaching solution, a fixing solution, a bleach-fixing solution or a combination thereof. In the processing of the present invention, if the bleaching solution is a bleaching solution, the solution is then treated with a fixing solution (fixing solution or bleach-fixing solution). In this case, the bleach-fix solution alone may be used. In order to further speed up the processing, a method of processing with a bleach-fixing solution after processing with a bleaching solution may be used.
The bleaching bath, the fixing bath and the bleach-fixing bath may be composed of two continuous baths, and the fixing treatment may be performed before the bleach-fixing treatment, or the bleaching treatment may be performed after the bleach-fixing treatment, depending on the purpose. It can be implemented arbitrarily. In the present invention, the case where the processing is performed with the bleaching solution and then the processing with the bleach-fixing solution or the fixing solution is most preferable. In the present invention, a ferric aminopolycarboxylic acid complex salt is used as a bleaching agent having a bleaching ability. Specific examples of the aminopolycarboxylic acid ferric complex are shown below, but the invention is not limited thereto. In addition, the oxidation-reduction potential is described. No. Compound Redox potential (mV vs. NHE, pH = 6) 1. N- (2-acetamido) iminodiacetic acid ferric complex 180 2. Methyl iminodiacetic acid ferric complex 200 3. Iminodiacetic acid second Iron complex salt 210 4. Ferric 1,4-butylenediamine tetraacetate complex 230 5. Ferric diethylene thioether diamine tetraacetate complex 230 6. Ferric glycol ether diamine tetraacetate complex 240 7. 1,3-propylene diamine Ferric tetraacetate complex 250 8. Ferric ethylenediaminetetraacetate complex 110 9. Ferric diethylenetriaminepentaacetate complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic ferric acid salt 80

The oxidation-reduction potential of the bleaching agent is determined by the method described in Transactions of the Faraday Society, Vol. 55 (1959), pp. 1312-1313. Is defined as the oxidation-reduction potential obtained by the measurement. In the present invention, the oxidation-reduction potential is set at 150 from the viewpoint of achieving the effect of the present invention while achieving both the effect of rapid processing and the effect of the present invention.
A bleach having a mV or more is preferred, and a bleach having a redox potential of 180 mV, most preferably 200 mV or more is more preferred. If the oxidation-reduction potential is too high, bleaching fog occurs, so the upper limit is 700 mV or less, preferably 500 mV or less. Also, ferric N- (2-carboxyphenyl) iminodiacetic acid complex, ferric complex 1,3-propylenediamine-N, N'-disuccinate, etc. have relatively strong oxidizing power and the bleaching agent of the present invention. Applicable as In the present invention, among these, compound No. 7, 1
Ferric 3-propylenediaminetetraacetic acid complex is particularly preferred.

The aminopolycarboxylic acid ferric complex salt is used as a salt of sodium, potassium, ammonium or the like.
Ammonium salts are preferred because of the fastest bleaching. The amount of the aminopolycarboxylic acid ferric complex salt used as a bleaching agent is suitably 0.01 to 1.0 mol per liter of a liquid having bleaching ability. Among these, the bleaching solution is preferably used in an amount of 0.01 to 0.7 mol per liter of the bleaching solution, and more preferably 0.15 to 0.7 mol per 1 liter of the bleaching solution in terms of speeding up processing and reducing stain with time. Particularly preferred is 0.30 to 0.6 mole. In the bleach-fix solution, the amount is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.2 mol, per liter of the bleach-fix solution. In the present invention, the bleaching agents may be used alone or in combination of two or more. When two or more bleaching agents are used in combination, the total concentration may be within the above range. When a ferric aminopolycarboxylic acid complex is used in the bleaching solution, it can be added in the form of a complex salt as described above, but the aminopolycarboxylic acid that is a complex-forming compound and a ferric salt (for example, Complex salts may be formed in the treatment liquid by coexisting with ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric sulfate, and ferric phosphate. In the case of this complex formation, the aminopolycarboxylic acid may be added slightly in excess of the amount required for complex formation with ferric ions, and usually 0.01 to 10% when added in excess. It is preferable to make the range excessive.

The treatment with the bleaching solution of the present invention is preferably carried out immediately after color development, but in the case of reversal treatment, the treatment is carried out via an adjusting bath (a bleach accelerating bath may be used). Generally. These adjustment baths may contain an image stabilizer described below. In the present invention, in addition to the bleaching agent, the liquid having bleaching ability is disclosed in
No. 144446, page (12), rehalogenating agents, pH buffers and known additives, aminopolycarboxylic acids, organic phosphonic acids, and the like can be used. Examples of the rehalogenating agent include sodium bromide and bromide. It is preferable to use potassium, ammonium bromide, potassium chloride or the like, and the content thereof is preferably 0.1 to 1.5 mol, more preferably 0.1 to 1.0 mol, per liter of a liquid having bleaching ability. It is particularly preferably 0.1 to 0.8 or less. In the present invention, it is preferable to use a nitric acid compound, for example, ammonium nitrate, sodium nitrate or the like, for the liquid having bleaching ability. In the present invention, the concentration of the nitric acid compound in 1 liter of the liquid having bleaching ability is preferably from 0 to 0.3 mol (including 0), more preferably from 0 to 0.2 mol (including 0). Usually, in order to prevent corrosion of stainless steel, a nitric acid compound such as ammonium nitrate or sodium nitrate is added. In the present invention, even if the amount of the nitric acid compound is small, corrosion hardly occurs and desilvering is good. In the present invention, various bleaching accelerators can be added to the bleaching solution or its pre-bath. Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858, German Patent 1,290,821, British Patent 1,138,842, and 53-95
No. 630, Research Disclosure No. 171
No. 29 (July, 1978), a compound having a mercapto group or a disulfide group, JP-A-50-140.
No. 129, thiourea derivatives described in US Pat. No. 3,706,561,
Iodides described in JP-A-58-16235, polyethylene oxides described in German Patent No. 2,748,430, polyamine compounds described in JP-B-45-8836, and the like can be used. . Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably, British Patent No. 1,
138,842 and JP-A-2-190856 are preferred.

The replenishing amount of the solution having the bleaching ability is 1 m ² of the photosensitive material.
50 to 500 ml is preferable, more preferably 8 to 500 ml.
It is 0 to 150 ml. The processing time when processing with a bleaching solution is preferably 3 minutes or less, particularly preferably from 10 seconds to 6 minutes.
0 seconds, most preferably 15 to 40 seconds. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air,
It is preferable to release air into the liquid through an air diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding the aeration, items described in Z-121, Using Process C-41, Third Edition (1982), pages BL-1 to BL-2, published by Eastman Kodak Company, can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is enhanced,
The contents described in page 8, upper right column, line 6 to lower left column, line 2 of JP-A-3-33847 can be used for the implementation.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, the emulsion surface of the photographic material described in JP-A-62-183460 or JP-A-3-33847, page 8, upper right column, line 6 to lower left column, second line can be used. A method of colliding a jet of a processing liquid,
A method of increasing the stirring effect using the rotating means of No. 62-183461, and further stirring by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface and causing the emulsion surface to become turbulent. A method for improving the effect and a method for increasing the circulating flow rate of the entire processing liquid can be given. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machines used for the light-sensitive material of the present invention are described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have the photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution. The solution having the bleaching ability of the present invention can be reused after collecting the overflow solution used for the treatment, correcting the composition by adding components, and then reusing the overflow solution. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (1990) issued by Fuji Photo Film Co., Ltd.
(Revised in August, 1999) The matters described on pages 39 to 40 can be applied.

Regarding the regeneration of the liquid having bleaching ability, a method described in "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona Co., 1979) and the like besides the aeration described above. Can be used. Specifically, in addition to electric field regeneration,
A method for regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, or the like can be used. In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. In addition, it is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. The solution having the bleaching ability of the present invention has an oxygen transmission rate of 1 cc / m ² .d during storage.
It is preferable to put in a closed container of ay.atm or more. Under these conditions, the effects of the present invention become more remarkable.

The color developing solution is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Representative examples of the color developing agent include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino -N-ethyl-N-β-hydroxyethylaniline, 4-amino-N-ethyl-N-γ-hydroxypropylaniline, 4-amino-N-ethyl-N-δ-hydroxybutylaniline, 3-methyl-4 -Amino-N-ethyl-N-β
-Methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a fog. It generally contains an inhibitor and the like. If necessary, various preservatives such as hydroxylamine, N, N-di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, catechol disulfonic acid, organic solvents such as diethylene glycol, benzyl alcohol, Development accelerators such as polyethylene glycol, quaternary ammonium salts and amines are added. Generally, the pH of these color developing solutions is 9 to 12.

The replenishing amount of the color developing solution depends on the photosensitive material to be processed, but is generally 1 liter or less per square meter of the photosensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. Preferably it is 50 ml to 400 ml / m ² . When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Common and, in particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution and the fixing solution, sulfites and bisulfites, benzenesulfinic acids (for example, sodium p-toluenesulfinate, m-carboxybenzenesulfinic acid), and carbonyl bisulfite adducts (for example, benzaldehyde- o-sulfonic acid bisulfite adduct) is preferred. It is preferable that the bleach-fixing solution or the fixing solution subsequent to the bleaching solution contains an imidazole compound in order to prevent poor color reproduction during running processing. In particular, a bleaching solution is a bleaching solution, and is effective in a solution having a subsequent fixing ability (fixing solution or bleach-fixing solution). Preferred imidazole compounds are unsubstituted imidazole and lower alkyl-substituted imidazole having 1 to 3 carbon atoms (eg, 2-methylimidazole, 3-methylimidazole and the like). A preferable addition amount of the imidazole compound is
The amount is 0.01 to 1 mol, more preferably 0.02 to 0.5 mol, per liter of the fixing solution or the bleach-fixing solution. The replenishing amount of the fixing solution is 100 to 1000 ml, preferably 150 to 300 ml, per m ² of the photosensitive material.

It is preferable to introduce a part or all of an overflow solution of a bath following the bath (for example, a washing bath or a stabilizing bath) into the solution having a fixing ability. The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Societies.
ety of Motion Picture and Television Engineers
64, p. 248-253 (May 1955),
You can ask. According to the multi-stage countercurrent method described in the literature, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank,
There is a problem that the generated suspended matter adheres to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, Japanese Patent Laid-Open No.
No. 8,542, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing, "Sterilization, Sterilization, and Antifungal Technology of Microorganisms" edited by the Sanitary Technology Association (1982), Industrial Technology Society, "Encyclopedia of Antifungal Agents" (ed. 1986)
Can be used.

In the processing of the photosensitive material of the present invention, washing water is used.
The pH is between 4 and 9, preferably between 5 and 8. The temperature of the rinsing water can be variously set depending on the characteristics of the photosensitive material, the application, and the like, but is generally from 15 to 45 ° C, preferably from 25 to 40 ° C. Further, the light-sensitive material of the present invention may be replaced with the above-mentioned water washing,
It can also be treated directly with a stabilizing solution. In such a stabilization process, JP-A-57-8543 and JP-A-58-14834 are used.
And the known methods described in JP-A-60-220345 can be used. Further, following the water washing process, a stabilization process may be further performed. As an example, a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photography may be mentioned. Can be. As dye stabilizers, aldehydes such as formalin and glutaraldehyde, N-methylol-1,2,4-triazole, N-
N-methylol compounds such as methylol pyrazole and dimethylol urea; hexamethylenetetramine, aldehyde sulfite adducts; azolylmethylamine compounds such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine; be able to. These dye stabilizers are described in JP-A-4-270344, JP-A-4-313753, JP-A-4-359249 and JP-A-5-3488.
No. 9, etc. Various chelating agents and fungicides can also be added to this stabilizing bath.

The light-sensitive material of the present invention undergoes washing and / or stabilizing steps after color development and desilvering. In the present invention, the total processing time of the water washing and / or stabilizing treatment is preferably 10 seconds or more and 60 seconds or less. In the water washing and / or stabilizing treatment, each treatment may be constituted by a plurality of treatment tanks, and even if the treatment is constituted by the plurality of treatment tanks, the total treatment time of these treatments is 20 seconds or more and 60 seconds or more.
Seconds or less. The replenishment amount of washing water and stabilizing solution is 1 m ^{2 for} photosensitive material.
Each is preferably 50 to 1000 ml, more preferably 100 to 400 ml.

In the light-sensitive material of the present invention, it is sufficient that at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer is provided on a support. The number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited. A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. , The photosensitive layer is blue light,
A unit photosensitive layer having color sensitivity to any of green light and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally a red-sensitive layer in order from the support side. , A green color sensitive layer and a blue color sensitive layer in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, see JP-A-61-4374.
No. 8, No. 59-113438, No. 59-113440
And couplers such as those described in JP-A-61-20037 and 61-20038, and may include a color-mixing inhibitor, an ultraviolet absorber, an anti-stain agent, and the like as commonly used. You may go out.

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, JP-A-62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.
As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /
Alternatively, they can be installed in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-63.
As described in JP-A-936-936, an order of blue-sensitive layer / GL / RL / GH / RH can be arranged from the side farthest from the support. In addition, Japanese Patent Publication No. 49-15495
The upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is halogenation having a lower sensitivity than the middle layer as described in Japanese Patent Publication An example is an arrangement in which a silver emulsion layer is arranged and the sensitivity is sequentially lowered toward the support, and the layer is composed of three layers having different sensitivities. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The dry thickness of the support of the light-sensitive material and all the constituent layers except the undercoat layer and the backing layer of the support is preferably from 12.0 to 20.0 μm from the viewpoint of bleaching fog, stain over time and the like. More preferably, 12.0-17.
0μ.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
The photosensitive material was stored under conditions of 5 ° C. and 50% RH for 7 days after the preparation, and firstly the total thickness of the photosensitive material was measured, and then the thickness of the coating layer on the support was removed and the thickness was measured again. The difference is used to determine the thickness of the entire coating layer excluding the support of the photosensitive material. The thickness is measured, for example, by a film thickness measuring device (Anritus Electric Co.
Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite. Further, a photograph of a cross section of the above-mentioned photosensitive material can be taken using a scanning electron microscope (preferably at a magnification of 3,000 or more), and the total thickness on the support can be measured.

In the present invention, the swelling ratio of the photosensitive material [(25
Equilibrium swollen film thickness in H ₂ O at 25 ° C., total dried film thickness at 25 ° C., 55% RH / total dried film thickness at 25 ° C., 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferred. If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the film swelling speed of the light-sensitive material in the present invention is defined as a saturated swelling film thickness which is 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds). When the time required to reach this 1/2 film thickness is defined as the swelling speed T1 / 2, it is preferable that T1 / 2 is 15 seconds or less. More preferably, it is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the light-sensitive material used in the present invention may be any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver bromide and silver chloride. Good.
Preferred silver halides are silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 0.1 to 30 mol% of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% iodide.

The silver halide grains of the photographic emulsion are cubic,
Those having regular crystals such as octahedron and tetrahedron,
Those having an irregular crystal form such as a sphere or a plate, those having a crystal defect such as a twin plane, or a composite form thereof may be used.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion preparation and types" and No. 18
716 (November 1979), p. 648, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glaf)
kides, Chimie et Physique Photographique Paul
Montel, 1967), Daffin's "Emulsion Chemistry",
Published by Focal Press (GF Duffin, Photographic
Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press (VLZelikman et alMakingand Coating).
Photographic Emulsion, Focal Press, 1964). U.S. Pat. Nos. 3,574,628 and 3,655,39
No. 4 and British Patent No. 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science, Inc.
And Engineering (Gutoff, Photographic Sci
14, 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, and 4,430,048;
No. 4,439,520 and British Patent No. 2,11
2,157 and the like.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a phase structure. Further, silver halides having different compositions may be joined by an epitaxial junction,
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure No. 17643 (December 1978) and No. 17643.
18716 (November 1979) and No. 307
105 (November 1989), and the relevant locations are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures (RD), and the relevant portions are shown in the following table. Type of additive [RD17643] [RD18716] [RD307105] 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right Columns 866 to 868 Super sensitizers to page 649 right column 4. Brightener 24 pages 647 page right column 868 5. Fogging prevention 24 to 25 pages 649 page right column 868 to 870 agents, stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers 7.Stain, page 25, right column, page 650, left column, page 872 Inhibitors-right column 8. Dye image, page 25 Page 650, left column, page 872 Stabilizer 9. Hardener page 26, page 651, left column, pages 874 to 875 10. Binder, page 26, page 651, left column, pages 873 to 874 11. Plasticizer, page 27, page 650, right column, page 876 Lubrication Agent 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static, page 27, 650, right column, pages 876 to 877 Inhibitor 14. MAT agent 878 to 879

In the present invention, various color couplers can be used in combination, and a typical example thereof is RD No. 1 described above.
7643, VII-CG and RD No. 307105, VII-CG
The patent is described in US Pat.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620;
Nos. 4,326,024 and 4,401,752
No. 4,248,961, JP-B-58-1073
9, UK Patent Nos. 1,425,020 and 1,47
No. 6,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and EP 249,473A are preferred.

As the magenta coupler, 2-equivalent and / or 4-equivalent 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. No. 4,310,619,
No. 4,351,897, European Patent 73,636
No. 3,061,432 and US Pat. No. 3,72.
No. 5,064, RD No. 24220 (June 1984
), JP-A-60-33552, RD No. 24230
(June 1984), JP-A-60-43659, 6
No. 1-72238, No. 60-35730, No. 55-1
Nos. 18034, 60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, WO (PCT) 88/047.
No. 95 is more preferable.

Cyan couplers include phenolic and naphthol couplers and are described in US Pat.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622 and 4,333,99.
No. 9, 4,753, 871, 4,451, 5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,29
No. 6,199, and JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in RD No. 17643, Sections VII-G,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,1
38,258, British Patent No. 1,146,368 and Japanese Patent Application No. 2-50137 are preferred. Also,
A coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a dye reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming as a leaving group.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084,820.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910 and British Patent 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
31,188, JP-A-59-157638, 59
The thing described in -170840 is preferable. Other couplers that can be used in the light-sensitive material of the present invention include a competitive coupler described in U.S. Pat. No. 4,130,427 and a dye capable of discoloring after disengagement described in EP 173,302A. Coupler, RDNo. 1144
No. 24241, bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, U.S. Pat.
No. 3,477, etc., ligand releasing couplers described in JP-A-63-75747, couplers releasing leuco dyes, couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181 and the like. Can be

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027 and the like. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-cyclohexyl phthalate). 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, etc.) Tridodecyl phosphate, tributoxyethyl phosphate,
Trichloropropylphosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide) , N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amyl phenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
Ert octylaniline and the like; hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used.
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of latexes for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230 and the like.
These couplers can be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the high boiling point organic solvent,
Alternatively, it can be dissolved in a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

The thickness of the support of the color negative film used in the present invention is preferably from 70 to 130 μm, and the material of the support is described in JP-A-4-124636, page 5, upper right column, first line to page 6, upper right. Various plastic films described in column 5, line 5 can be used, and preferred are cellulose derivatives (eg, diacetyl-, triacetyl-,
Propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (eg, polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate,
Polyethylene naphthalate). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The support of the color negative film used in the present invention includes a support having a conductive layer and a transparent magnetic material layer on one surface as described in JP-A-4-62543.
International Patent Publication WO90 / 04205, FIG. 1
A having a magnetic recording layer described in A.
No. 124628, which has a stripe magnetic recording layer,
In addition, those having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer are also preferable. It is preferable to provide a protective layer described in JP-A-4-73737 on these magnetic recording layers. The package (patrone) for accommodating the color negative film of the present invention may be of any type currently used or known, and in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred.

[0047]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. (Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: sensitizing dye The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² units for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 HBS-1 0.30 HBS-2 1.2 × 10 ^-2

Second layer: Intermediate layer Fine grain silver iodobromide (AgI: 1.0 mol%, equivalent sphere diameter: 0.7 μm)
m) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2

Third layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A silver coating amount 0.42 silver iodobromide emulsion B silver coating amount 0.40 gelatin 1.90 ExS-1 6.8 × 10 ^-4 mol ExS-2 2.2 × 10 ^-4 mol ExS-3 6.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 HBS-1 0.32

Fourth layer: middle-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion C Silver coating amount 0.85 Gelatin 0.91 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.5 × 10 ^{− 5} mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 HBS-1 0.10

Fifth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver coating amount 1.50 Gelatin 1.20 ExS-1 3.0 × 10 ^-4 mol ExS-2 9.0 × 10 ^-5 mol ExS-3 3.0 × 10 ^{− 5} mol ExC-2 8.5 × 10 ^-2 ExC-5 3.6 × 10 ^-2 ExC-6 1.0 × 10 ^-2 ExC-7 3.7 × 10 ^-2 HBS-1 0.12 HBS-2 0.12

Sixth layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 × 10 ^-2 HBS-1 8.0 × 10 ^-2

Seventh layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion E Silver coating amount 0.28 Silver iodobromide emulsion F Silver coating amount 0.16 Gelatin 1.20 ExS-4 7.5 × 10 ^-4 mol ExS-5 3.0 × 10 ^-4 mol ExS-6 1.5 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 HBS-1 0.20 HBS-3 3.0 × 10 ^-2

[0055] Eighth layer: middle sensitivity green-sensitive emulsion layer Silver iodobromide emulsion G silver laydown 0.57 Gelatin 0.45 ExS-4 5.2 × 10 ^-4 mol ExS-5 2.1 × 10 ^-4 mol ExS-6 1.1 × 10 ^{- 4} mol ExM-1 0.12 ExM-2 7.1 × 10 ^-3 ExM-3 3.5 × 10 ^-2 HBS-1 0.15 HBS-3 1.0 × 10 ^-2

Ninth layer: Intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2

Tenth layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ^-4 mol ExS-5 1.2 × 10 ^-4 mol ExS-6 1.2 × 10 ^{− 4} mol ExM-4 5.8 × 10 ^-2 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 HBS-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

Twelfth layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10

13th layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion I Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 HBS-1 0.15

Fourteenth layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion J Silver coating amount 0.19 Gelatin 0.35 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.22 HBS-1 7.0 × 10 ^-2

Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

Sixteenth layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion K Silver coating amount 1.55 Gelatin 1.00 ExS-8 2.2 × 10 ^-4 mol ExY-1 0.21 HBS-1 7.0 × 10 ^-2

17th layer: 1st protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 HBS-1 1.0 × 10 ^-2 HBS-2 1.0 × 10 ^-2

18th layer: 2nd protective layer Fine particle silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (1.5 μm diameter) 2.0 × 10 ^-2 B-2 (1.5 μm diameter) 0.15 B -3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

The samples thus prepared include, in addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. further,
B-4 to B-6, W-2, W-3, F-1 to F
-15, iron salts, lead salts, gold salts, platinum salts, iridium salts, rhodium salts and palladium salts.

[0067]

[Table 1]

In Table 1, (1) Each emulsion was subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-19938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. I have. (3) For preparing tabular grains, low molecular weight gelatin was used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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The above multilayer color photosensitive material sample 101 was
Those taken by cutting and camera 5mm width was subjected to the following processing for one day 1 m ² by 15 days. (Running processing) Each processing was performed by an automatic processor FP-5 manufactured by Fuji Photo Film Co., Ltd.
60B was partially modified so that the following processing steps were performed. The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 15 ml 17 liter Bleaching 40 seconds 38.0 ° C 5 ml 5 liters Fixing (1) 50 seconds 38.0 ° C -5 Liter Settling (2) 50 seconds 38.0 ° C 8 ml 5 liter Washing water 30 seconds 38.0 ° C 17 ml 3.5 liter Stability (1) 20 seconds 38.0 ° C-3 liter Stability (2) 20 seconds 38.0 ° C 15 ml 3 liter Dry Drying 1 minute 30 seconds 60 ° C * Replenishment amount per photosensitive material 35 mm width 1.1m (equivalent to 24 Ex. 1 bottle) Stabilizing solution and fixing solution are countercurrent type from (2) to (1), and washing water is used. All the overflow solution was introduced into the fixing bath. The amount of the developer brought into the bleaching step, the amount of the bleached liquid brought into the fixing step, and the amount of the fixer brought into the water washing step were 2.times.
5 ml, 2.0 ml, and 2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.4 2.4 1,2-Dihydroxy-3,5-0.3 0.3 Disodium disulfonate Sodium sulfite 3.9 5.5 Potassium carbonate 37.5 39.0 Potassium bromide 1.4-Iodine Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.7 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.8 Add water 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.21

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 120 180 Ammonium bromide 70 105 Ammonium nitrate 14 21 Organic acid (Table A) Table A 1.5 liters of the tank liquid Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.4 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 1953 Ammonium thiosulfate aqueous solution (750 g / L) 250 mL 690 mL Ammonium methanethiosulfonate 40 112 Ethylenediaminetetraacetic acid 15 42 Add water and add 1.0 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.4 7.45

(Washing water) Tap water was replaced with an H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 1,2-benzoisothiazoline-3- on. Sodium salt 0.05 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water and add 1.0 liter pH 8.5

(Evaluation of Desilvering Property) At the end of each of the above-mentioned running processes, the sample 101 was subjected to a color temperature of 4800K and 500C.
Those exposed to MS were processed, and the amount of residual silver after the processing was analyzed by X-ray fluorescence. Those having a small amount of residual silver are preferred in terms of desilverability. (Evaluation of Stain) The sample 101 was processed at the start and end of the running process, and the yellow density of the unexposed portion was measured with a photographic densitometer FSD-1 manufactured by Fuji Photo Film Co., Ltd.
03, and the density at the start and the density increase due to running (density at the end-density at the start) were determined. The starting concentration depends on the degree of bleaching fog, the lower the value, the better. The increase in density due to running is considered to be contamination due to the introduction of the developer, and the smaller the increase in density, the better.

(Evaluation of low-temperature precipitation property) Each bleaching replenisher was placed in a flexible container made of polyethylene (capacity: 2 liters), stored at 0 ° C for 2 weeks, and filtered with a filter paper to confirm the presence or absence of a precipitate. The evaluation criteria are as follows. ＝ = no precipitate △ = slightly powdery precipitate observed (1 g or less) × = crystalline precipitate observed (evaluation of odor) 500 ml of each bleaching replenisher was placed in a beaker at room temperature Was evaluated for odor. The evaluators made 10 evaluations according to the following criteria, and the evaluation with the largest number of people was taken as the evaluation result. ＝= No odor at all △ = Slight odor but barely noticeable × = Clear odor Evaluation results are shown in Table A.

[0092]

[Table 2]

[0093]

[Table 3]

As can be seen from the results, by using two or more kinds of the organic acids of the present invention, desilvering is good, no odor is caused, and increase in stain due to low-temperature precipitation, bleaching fog and running can be prevented.

Embodiment 2 In the case of No. 1 in Embodiment 1, In the treatments 1 and 14, the amount of ammonium nitrate in the bleaching solution was reduced as shown in Table B, and the desilvering property and the metal corrosion property were examined. However, the processing was carried out in the same manner as in Example 1 except that the bleaching treatment time was 35 seconds. For metal corrosion, each bleaching solution was kept at 60 ° C and stainless steel (SU
After immersing the chip of S316) and 30 days have passed,
Metal corrosion on the stainless steel surface near the interface between the bleaching solution and air was visually evaluated. Evaluation criteria ＝ = No corrosion was observed 曇 = Fogging was observed on the stainless steel surface near the gas-liquid interface × = Rust was observed on the stainless steel surface near the gas-liquid interface The results are shown in Table B.

[0096]

[Table 4]

It can be seen that by reducing the concentration of the nitrate compound in the bleaching solution, the desilvering property can be improved, and that in the processing solution of the present invention, even if the nitrate compound is reduced, the metal corrosion does not deteriorate.

Embodiment 3 In the first embodiment, as shown in FIG. 18 and no. In the processing of 20,
Exactly the same processing was performed except that imidazole was added to the fixing solution at 15 g / l and the fixing replenisher at 42 g / l (Nos. 21, 22). At the end of the running, the cyan density of the sample treated with the same exposure as in the evaluation of desilvering property was measured. Nos. 21 and 22 are No. 18 and no. 0.5 in cyan density than 20
It was found to be high and excellent in recolorability.

Embodiment 4 In the case of No. 1 in Embodiment 1, 21 and No. 21. In the process of 22,
The multilayer color photographic material sample 101 was prepared as described in JP-A-5-18855.
Evaluation was made in the same manner except that the photosensitive material sample 101 of No. 0 Example 1 was changed. As a result, it was confirmed that the results were excellent in desilvering property, prevention of increase in stain concentration, and recoloring property.

[0100]

According to the present invention, two or more of succinic acid, glutaric acid, and adipic acid are added to a processing solution having a bleaching ability of pH 2 to 5.5 containing an aminopolycarboxylic acid ferric complex bleaching agent. By containing the three types, good results were obtained in any of desilvering, bleaching fog, stain increase due to running, odor of replenisher and low-temperature precipitation.

Claims (4)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material with a solution having a bleaching ability, wherein the solution having the bleaching ability contains a ferric aminopolycarboxylic acid complex salt as a bleaching agent and has a pH of A method for processing a silver halide color photographic light-sensitive material, which further comprises two or three of succinic acid, glutaric acid and adipic acid. 2. A method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein said liquid having bleaching ability contains all three of succinic acid, glutaric acid and adipic acid. 3. The method according to claim 1, wherein the bleaching solution contains a nitric acid compound at a concentration of 0 to 0.3 mol (including 0) per liter of the bleaching solution. 2. The method for processing a silver halide color photographic light-sensitive material according to item 2. 4. The bleaching solution having a bleaching ability,
4. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein an imidazole compound is contained in a liquid having a fixing ability subsequent thereto.