JPH06130613A - Stabilizing solution and rinse solution for silver halide color photographic sensitive material and processing method using them - Google Patents

Abstract

PURPOSE:To prevent putrefaction and an adverse effect on photographic performance and to improve handleability by incorporating at least one kind of aminoglycoside group, such as gentamycin, amicacin, or tobramycin. CONSTITUTION:The stabilizing solution or rinse solution to be used contains at least one kind of aminoglycoside selected from gentamycin, amikacin, tobramycin, dibekacin, micronomycin, isepamycin, sisomycin, netylmycin, and astromycin. The rinse solution does not mean here to feed the solution at a constant flow rate but to replenish the rinse solution in accordance with the processing amount of the photosensitive material. A small amount of salt, such as sodium or potassium sulfate, or a chelating agent, such as ethylenediamine tetraacetate, is added to the rinse solution, when needed, in order to rinse efficiency, and the disinfectant effect on the rinse solution can be kept up for a long period by adding such an aminoglycoside to the stabilizing solution containing no formaldehyde.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing solution, a rinsing solution and a processing method using the same, which are used for processing a silver halide color photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material). .

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is imagewise exposed and then color-developed. A silver halide color reversal photographic light-sensitive material is subjected to imagewise exposure, black-and-white development, reversal processing, and then color development processing. The color development process comprises a color development process and a subsequent desilvering process. The desilvering process generally consists of a bleaching process and a fixing process. Here, the bleaching treatment and the fixing treatment may be a bleach-fixing treatment performed in one bath, or a bleach-fixing treatment may be provided between the bleaching treatment and the fixing treatment.

The image-formed light-sensitive material is washed with water, rinsed and / or rinsed after desilvering because of the storability of the obtained image.
Alternatively, stabilization processing is performed. The water washing process is a process of effectively washing out the processing chemicals from the photosensitive material. The rinsing process is a process called rinsing rinsing in which the washing water is not supplied at a constant flow rate but is replenished with water according to the processing amount of the light-sensitive material, and the amount of water used is reduced. . In addition to using mere water for this rinsing and rinsing, additives that improve the efficiency of rinsing as needed, for example, trace amounts of salts such as sodium sulfate and potassium sulfate, or trace amounts of chelating agents such as ethylenediaminetetraacetic acid (EDTA) are used. Is also added. The stabilizing process is a processing solution containing an image stabilizer for preventing image deterioration, and examples thereof include a stabilizing solution used in the final bath in the processing of a color negative film or a color reversal light-sensitive material. For color reversal light-sensitive materials, there has been proposed an adjusting stabilizer containing an image stabilizer in a processing solution called an adjusting solution used between the color development step and the desilvering step. For more information on these processing steps, see James, "The Theory of
It is also described in Photographic Process "4'th Edition (1977).

In recent years, from the viewpoint of environmental protection, there has been a strong demand for reduction of photographic waste liquid, and low replenishment of treatment is being promoted. Even in washing and stabilizing baths, it is close to a new liquid during continuous treatment. The conventional treatment with a large amount of replenisher, which can be treated with a liquid, has been replaced with a treatment with a small amount of replenisher. However, when the replenishment amount of the washing or rinsing liquid or the stabilizing liquid is lowered, these treatment liquids stay in the treatment tank for a long period of time, which causes a problem of spoilage of the liquids. The rinse solution and stabilizing solution are different from the color developing solution and other processing solutions in that the salt concentration of the solution is low, and because they are in an environment where bacteria and mold easily grow, the rinse solution and stabilizer are often contaminated by bacteria and mold. It causes problems such as turbidity, or decomposition of processing chemical components.

In order to address these problems, antibacterial agents,
The addition of anti-fungal agents has been proposed. For example, thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds, diazines and triazine compounds, Journal Antibacterial & thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride
Antifungus Agent (J. Antibact. Ant
ifung. Agents) Vol 1. No. 5, p. 207 to 223 (1
983), a general-purpose antibacterial / antifungal agent and the like.

[0006]

However, there is a problem in that the antibacterial agent known to be used in the processing solution for the light-sensitive material is not effective unless it is added in a large amount. Further, it has been found that a new problem occurs when combined with a low replenishment of the color developing solution, that is, a problem of contamination of the color developing solution by the stabilizing solution component or the rinse solution component. In the cine type developing machine, the leader joined to the processed film is dried as it is after passing through the final bath together with the film. In this way, the leader having the stabilizer or rinse bath component of the final bath attached thereto is reused without being washed, so that the attached stabilizer component is brought into the developer. Similarly, in the hanger type developing machine, the same phenomenon occurs when the film is attached to the film hanger. As a result of the extremely low replenishment of the color developing solution, this accumulated concentration increases, so that the conventional antibacterial agent contained in the stabilizing solution or the rinsing solution may adversely affect the photographic properties such as fog and sensitivity deterioration. understood.

Therefore, a first object of the present invention is to provide a stabilizing solution, a rinsing solution, and a treatment method using the same, which do not cause spoilage even when the replenishment rate is lowered and which are excellent in handleability. . Further, a second object of the present invention is to provide a stabilizing solution, a rinsing solution and a processing method using the same, which have no adverse effects on photographic properties (for example, decomposing the image stabilizer) and prevent spoilage. It is in. Further, a third object of the present invention is to bring into a color developing solution, and even when the replenishment of the color developing solution is reduced, a stabilizing solution, a rinsing solution and a stabilizing solution which do not adversely affect the photographic properties such as fog generation and sensitivity deterioration. It is to provide a processing method using.

[0008]

[Means for Solving the Problems] The above-mentioned problems are gentamicin (Gentamicin), amikacin (Amikacin), tobramycin (Tobramicin), dibekacin (Dibekacin), micronomycin (Micronomicin), isepamicin (Isepamici)
n), Sisomicin, Netilmycin (Netil
micin) and astromicin (Astromicin), at least one kind of aminoglycoside (hereinafter referred to as amicoglycoside of the present invention) is contained, a rinse solution, a stabilizing solution, and a silver halide color photograph using them. It has been solved by a method of processing a light-sensitive material.

The present invention will be described in detail below. The rinsing liquid in the present invention is a processing liquid for rinsing so-called rinsing water in which the washing water is not supplied at a constant flow rate but is replenished in an amount corresponding to the processing amount of the light-sensitive material. The rinse liquid basically uses simple water, and if necessary, additives such as trace amounts of salts of sodium sulfate, potassium sulfate, etc., or trace amounts of ethylenediaminetetraacetic acid (EDTA) are added to improve washing efficiency. A chelating agent can also be added. Further, a surfactant may be contained in order to prevent unevenness of water drops during drying. The stabilizing solution in the present invention refers to a processing solution and a replenishing solution thereof for preventing the deterioration of a color image such as a color negative film and a color reversal film, and in addition to the stabilizing solution used as a final bath after the desilvering process. It also contains an adjusting stabilizer such as a color reversal film.

The amicoglycosides of the present invention will be described. The amicoglycosides of the present invention are known as preservatives. For example, gentamicins are described in U.S. Pat.Nos. 3,091,572 and 3,136,704, amikacin in U.S. Pat.No. 3,781,268, isepamicin in U.S. Pat.No. 4,002,742, micronomycin in U.S. Pat. 2,326,781, U.S. Pat. Nos. 4,002,742 and 4,029,882 for netilmicin, German Patent No. 2,
437,160, U.S. Pat.
No. 286 can be referred to. Specific examples of gentamicin are shown below.

Compound No. 1 Gentamicin A ₂ 2 Gentamicin A 3 Gentamicin A ₁ 4 Gentamicin B 5 Gentamicin X ₂ 6 Antibiotic JI-20A 7 Gentamicin B ₁ 8 Antibiotic G418 9 Antibiotic JI-20B 10 Gentamicin C ₁ 11 Gentamicin C _1a 12 Gentamicin C ₂ 13 Gentamicin C _2a 14 Gentamicin C _2b

The aminoglycosides of the present invention are commercially available as preservatives and antibacterial agents, and commercially available products can be used.
And for these properties, The Merck Index
(The Merck Index) 11th Edition (1989) MERCK & Co., INC.
It is described in. Among the aminoglycosides of the present invention, gentamicin is particularly preferable. The aminoglycoside of the present invention may be added to the stabilizing solution or the rinsing solution at the time of use, or may be contained in the concentrated stabilizing solution in advance. The addition amount is 1 ppm to 100 ppm in a stabilizing solution or a rinse solution as a final use solution, preferably 3 to 5
It is 0 ppm. In many cases, the stabilizing solution is supplied as a concentrated stabilizing solution and diluted at the time of use. The amount of the compound of the present invention added in the concentrated stabilizing solution is 30 ppm to 10000 pp.
m, preferably 300 to 3000 ppm.

It has also been found that when the aminoglycosides of the present invention are contained in a stabilizing solution containing substantially no formalin, the antibacterial effect of the solution lasts for a long time and more preferable results are obtained. That is, the stabilizer of the present invention may contain any image stabilizer, but in the present invention, substantially no formalin is contained, and the effect is obtained when an image stabilizer other than formalin is used. Greatly preferred.
In the present invention, the phrase "substantially free of formalin" means that the concentration of free formaldehyde in the liquid is 0.01% or less, and more preferably 0.005.
% Or less.

As image stabilizers other than formalin,
Any known one can be used. As image stabilizers other than formalin, JP-A-63-244036 is known.
In the publication, hexamethylenetetramine compounds are described. In addition, many N-methylol compounds having a specific structure have been proposed. For example, US Pat.
487,569 and N-methylol compounds of melamine compounds of US Pat. No. 2,629,660, US Pat. No. 2,57.
Urea of 9,435, N- of 2-oxapropylene urea
Methylol compound, US Pat. No. 2,487,446,
N-methylol compounds of thiourea compounds of Japanese Patent Publication No. 458506, N-methylol compounds of hydantoin compounds of US Pat. No. 2,579,436, British Patent No. 684,540, and British Patent No. 908,136. N-methylol compounds of cyandiamide compounds, US Pat.
No. 801,322, N-methylol compounds of guanidine compounds described in JP-A-61-35447, British Patent No. 1,39
2,134, Morpholine, N-methylol compounds of biuret compounds, N-methylol compounds of pyrrole, pyrrolidine, methylamine, glycine and ethylcarbamate of JP-A-2-153348 are known.

Particularly preferable N-methylol is pyrazole, 1,2,2, described in JP-A-4-270344.
Mention may be made of 4-triazole N-methylol compounds. Also, regarding the usage of these compounds,
U.S. Pat. Nos. 4,786,583 and 4,859,5
No. 74, No. 4,921, 779, European Patent No. 3
No. 45,172, No. 395,442, and the like. Further, an azolylmethylamine compound is also effective. Particularly, the azolylmethylamine compound described in European Patent Publication No. 050409A2 is particularly preferable because it does not generate free formaldehyde gas and has a high dye image stabilizing effect. Further, these are preferably used in combination with azoles such as pyrazole and 1,2,4-triazole. In addition, an aliphatic or aromatic aldehyde can be used as an image stabilizer. Specific examples of the formalin substitute are shown below, but the present invention is not limited thereto.

[0016]

[Chemical 1]

[0017]

[Chemical 2]

A-23 hexamethylenetetramine A-24 N-methylolurea The content of these image stabilizers is preferably 0.001 to 0.01 mol per liter of the stabilizing solution, and 0.00
1 to 0.05 mol is more preferable. When the stabilizing solution or rinsing solution of the present invention is set as the final bath of the treatment, it is preferable to add a surfactant in order to prevent uneven drying of the film. Any surfactant can be used. For example, polyethylene glycol type nonionic surfactant, polyglycidyl type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester salt type Anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surface active agent Although there is an activator, it is preferable to use a nonionic surfactant, and in particular, an alkylphenol ethylene oxide adduct and an alkylphenol glycidol adduct are preferable from the viewpoint of preventing film stains and water-spot. As the alkylphenol, octylphenol, nonylphenol, dodecylphenol and dinonylphenol are particularly preferable, the number of moles of ethylene oxide added is particularly 8 to 14, and the number of moles of glycidol added is particularly preferably 6 to 13. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect. Examples of preferable surfactants are shown below, but the present invention is not limited thereto.

[0019]

[Chemical 3]

The amount of surfactant added is 0.005 g to 3 g, preferably 0.02 g per liter of the stabilizing solution.
It is 0.3 g. The stabilizing solution of the present invention may further contain an organic acid or a pH buffer. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, and alkanolamines described in US Pat. No. 4,786,583 can be used.

Further, the stabilizing solution of the present invention preferably contains various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysis products of maleic anhydride polymers described in European Patent 345172A1. The pH of the stabilizing solution of the present invention is usually in the range of 4.0 to 10, preferably 5.0 to 9.0, more preferably 6.
It is 5 to 8.6.

The composition of the stabilizing solution of the present invention can be maintained by supplying a fixed amount of the replenishing solution depending on the treatment.
The composition of the replenisher is set so as to correct the consumption of the active ingredient associated with the treatment, the dilution of the solution brought in from the previous bath, and the like.
Usually, the replenisher is supplied at a concentration of 10 to 200 times that of the stable replenisher, and the replenisher is divided into a plurality of concentrates and supplied, and the plurality of concentrated compositions are mixed and diluted to obtain a replenisher. You may do it. Concentration is preferably 15 to 300 times
Times, and more preferably 50 times to 150 times. In the case of continuous processing using the stable replenishing solution of the present invention, it is preferable to replenish with 100 to 1700 ml per 1 m ² of the light-sensitive material, more preferably 200 to 650 ml, and particularly preferably 200 to 580 ml. The stabilizing solution of the present invention is generally used in the final step following the usual color developing and desilvering steps, but it is not necessarily limited to this. Regarding the processing formulation and the processing steps such as the color development step, the desilvering step, the water washing step, etc.
No. 466545 and the like.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. Preferred aromatic primary amine color developing agents are p-phenylenediamine derivatives such as N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5-. (N-ethyl-N
-Laurylamino) toluene, 4- [N-ethyl-N-
(Β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl)
Amino] aniline, 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p
-Phenylenediamine, 4-amino-3-methyl-N-
Ethyl-N-methoxyethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline and the like can be mentioned. Of these, particularly preferred is 2-methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino] aniline. Further, these p-phenylenediamine derivatives are sulfates,
It may be a salt such as hydrochloride, sulfite or p-toluenesulfonate. The amount of the aromatic primary amine color developing agent used is 0.001 to 0.
A concentration of 1 molar is preferred, more preferably 0.01-
The concentration is 0.06 molar.

Further, as a preservative for the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfite salts such as potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. The preferred amount of preservative added is 0.5 to 10 g, and more preferably 1 to 5 g, per liter of color developer. Further, various hydroxylamines (for example, JP-A-63-63) are used as compounds for directly preserving the aromatic primary amine color developing agent.
Compounds described in 5341 and 63-106655,
Of these, compounds having a sulfo group or a carboxy group are preferable. ), Hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A 63-146041, 63-44657 and 63-584.
It is preferable to add phenols described in No. 43, α-hydroxyketones and α-aminoketones described in 63-46656 and / or various sugars described in 63-36244. In addition, in combination with the above compounds, JP-A Nos. 63-4235, 63-24254 and 63-2
1647, 63-146040, 63-278.
41 and 63-25654 and the like, monoamines, 63-30845, 63-14640,
Diamines described in 63-43139 and the like, 63-
21647, 63-26655 and 63-4
4655, polyamines, 63-53551, nitroxy radicals, 63-43140 and 63-53549, alcohols, 63-
56654 and oximes and 63-2394
It is preferable to use the tertiary amines described in No. 47.

Other preservatives are disclosed in JP-A-57-441.
48 and 57-53749, various metals, salicylic acids described in JP-A-59-180588,
Alkanolamines described in JP-A-54-3582,
Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution contains compounds of other known developing solution components. be able to. In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer 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), Examples thereof include potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffering agent added to the color developing solution is preferably 0.1 mol / liter or more, particularly 0.1 to 0.1 mol / liter.
Particularly preferred is 0.4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing precipitation of calcium or magnesium or for improving the stability of the color developing solution. The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Representative examples of these are nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'.
-Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4- Examples thereof include tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid and the like. 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 color developing solution, for example, 1
It is about 0.1 g to 10 g per liter.

If desired, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication Nos. 37-16088, 37-5987 and 38
-7826, 44-12380, 45-901.
9, thioether compounds described in U.S. Pat. No. 3,818,247, etc., p-phenylenediamine compounds described in JP-A Nos. 52-49829 and 50-15554, and JP-A No. 50-137726. No.
0074, JP-A-56-156826, JP-A-52-4
Quaternary ammonium salts described in 3429, U.S. Pat. Nos. 2,494,903 and 3,128,182,
No. 4,230,796, No. 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
No. 2,546, No. 2,596,926, No. 3,5
82,346, etc., amine compounds, JP-B-37
-16088, 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication Nos. 41-11431, 42-23883, U.S. Pat. No. 3,532,501, and the like, polyalkylene oxides, In addition, 1-phenyl-3-pyrazolidones, imidazoles and the like can be added if necessary.

In the present invention, if necessary,
Any antifoggant can be added. 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-
Nitrogen-containing substances such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. A heterocyclic compound can be given as a representative example.

The processing temperature of the color developing solution in the present invention is
It is 20 to 50 ° C, preferably 30 to 45 ° C. During processing
The time is 1 minute to 5 minutes, preferably 1 minute 30 seconds to 3 minutes 20 seconds
Yes, and more preferably 1 minute to 2 minutes and 30 seconds. Starting
In light, the replenishment amount of the color developing solution is 1 m²This
Although it is 85 to 120 ml, the effect of the antibacterial agent of the present invention
This replenishment rate is 300-660 ml / m ², Especially 30
0-430m²It is especially remarkable in. Phosphorus of the present invention
Solution, stabilizing solution, and processing using it are optional photosensitive materials.
Is especially applicable for color negative photography
Applicable to light-sensitive materials or color reversal photographic light-sensitive materials.
And, the effect is exerted greatly. These photosensitive materials
Regarding the above, Japanese Patent Laid-Open Nos. 3-46654 and 2-854.
No. 2-90151, 4-270344, Europe
It is described in Japanese Patent Publication No. 0504609A. Shooting
Color negative photographic light-sensitive material for shadow or color reversal photographic feeling
Silver iodide is used as the silver halide used for optical materials.
Silver iodobromide containing 0.2 to 20 mol% is preferable.

[0031]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Example 1 (Bacterial reproduction test) A stable replenisher having the following composition was prepared. N, N'-bis (1,2,4-triazole-1-0.56g ylmethyl) piperazine (image stabilizer) 1,2,4-triazole 1.25g polyethylene glycol nonyl phenyl ether (degree of polymerization 10) 0 0.25 g ethylenediaminetetraacetic acid 0.04 g Water was added to 1 liter pH 8.4

This was used as stable replenisher 1, and the preservatives of the present invention shown in Table 1 were added thereto, and stable replenishers 2 to 7 having the same composition as this were prepared. In addition, for comparison, JP-A-6
Antibacterial agent A described in 1-35446 and JP-A-57-85
Stable replenishers 8 to 13 containing the antibacterial agent B described in No. 41 were prepared.

[0033]

[Chemical 4]

Fuji Photo Film Co., Ltd. automatic processor FP
-350 was filled with a starting solution of the treating agent CN-16Q manufactured by the same company. However, the above-mentioned blank stable replenisher was filled in the stabilizing bath. In the same manner, the color negative film, SHG-100, was replenished at a rate of 20 per day for 2 weeks while supplementing to obtain a running solution. 10 ml of this running solution was added to 100 ml of each of the above stable replenishers, placed in a constant temperature air bath at 30 ° C., allowed to stand, and sampled at 3 days, 1 week, and 2 weeks to determine the residual ratio of the image stabilizer. A simple culture medium (trade name: Easicult ^R , ORIN DI
AGNOSTICA). Table 1 shows the number of bacteria and the judgment level, and Table 2 shows the test results.

[0035]

[Table 1]

[0036]

[Table 2]

In the case of a blank containing no antibacterial agent, the growth of the bacteria is remarkable and the image stabilizer is decomposed, whereas when the known antibacterial agent is added, the growth of the bacteria is suppressed, A high addition concentration is required and the effect is incomplete. On the other hand, when the compound according to the present invention is added, a sufficient amount of the antibacterial effect can be obtained, the liquid does not become slimy, and the image stabilizer is not decomposed.

Example 2 (Contamination Test of Developer) On a subbed cellulose triacetate film support,
A color negative film 201 composed of each layer having the composition shown below was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The coating amount is g for silver halide and colloidal silver.
/ M ² units of silver, for couplers, additives and gelatin the amounts in g / m ² units, for sensitizing dyes the moles per mole of silver halide in the same layer. It is shown by the number.

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 silver iodobromide (AgI 1.0 mol%, sphere equivalent diameter O.O7myuemu) silver coverage 0.15 gelatin ^{1.00 ExC-4 6.0 × 10 -2} Cpd-3 2.0 × 10 - ² 3rd 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 x 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 x 10 ^-2 ExC-4 2.3 x 10 ^-2 HBS-1 0.32

Fourth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Silver Iodobromide Emulsion C Silver Coating Weight 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} mols 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 x 10 ^-2 ExC-7 3.7 x 10 ^-2 HBS-1 0.12 HBS-2 0.12 6th layer: Intermediate layer Gelatin 1.00 Cpd-4 8.0 x 10 ^-2 HBS-1 8.0 x 10 ^-2

Seventh layer: low-sensitivity green 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 Eighth layer: Medium-speed green emulsion layer 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 x 10 ^-2 HBS-1 0.15 HBS-3 1.0 x 10 ^-2

Ninth layer: Intermediate layer Gelatin 0.50 HBS-1 2.0 × 10 ^-2 Tenth layer: High sensitivity green emulsion layer Silver iodobromide emulsion H Silver coating amount 1.30 Gelatin 1.20 ExS-4 3.0 × 10 ^-4 mol ExS-5 1.2x10 ^-4 mol ExS-6 1.2x10 ^-4 mol ExM-4 5.8x10 ^-2 ExM-6 5.0x10 ^-3 ExC- ² 4.5x10 ^-3 Cpd-5 1.0x10 ^-2 HBS-1 0.25 11th layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 HBS-1 0.12

12th layer: Intermediate layer Gelatin 0.45 Cpd-3 0.10 13th layer: Low-sensitivity blue 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 14th layer: Medium speed blue 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 x 10 ^-2

Fifteenth layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent spherical diameter O.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: High-sensitivity blue-sensitive emulsion layer Iodobromide Silver 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 x 10 ^-2 HBS-2 1.0 x 10 ^-2

Eighteenth layer: Second protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5 μm) 2.0 × 10 ^-2 B-2 (diameter 1.5 μm) 0.15 B -3 3.0 × 10 ^-2 WA-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00 In addition to the above, 1,2-benzisothiazolin-3-one (relative to gelatin) 20 on average
0 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Further, B-4 to B-6, WA-2, WA-3, F-1 to F-1
5, iron salt, lead salt, gold salt, platinum salt, iridium salt, rhodium salt and palladium salt are contained.

[0046]

[Table 3]

In Table 3, (1) Each emulsion was reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (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. There is. (3) For the preparation of tabular grains, low molecular weight gelatin is 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 by using a high voltage electron microscope.

[0048]

[Chemical 5]

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

[Chemical 8]

[0052]

[Chemical 9]

[0053]

[Chemical 10]

[0054]

[Chemical 11]

[0055]

[Chemical 12]

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

The color negative film 201 thus prepared was slit into a width of 35 mm and subjected to an experiment.
Processing was performed while replenishing using a small cine type automatic processor. Before and after the color negative film 201, a leader having a length of 10% was joined, and after the treatment, the leader was removed from the film and reused without washing. In this way, the processing was continued until the liquid in the developer tank was replaced twice.

Processing step Processing time Processing temperature Replenishment amount * Tank capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38.0 428 2 Bleach 3 minutes 38.0 140 2 Fixing 3 minutes 38.0 400 2 Washing with water (1) 45 seconds 38.0-1 Washing with water (2) 1 minute 30 seconds 38.0 400 ml / min 1 Stable 45 seconds 38.0 570 1 Drying 120 seconds 55 * Replenishment amount per 1 m ² of photosensitive material The amount of water is a countercurrent method from (2) to (1). The amount of the developing solution brought into the bleaching step and the amount of the bleaching solution brought into the fixing step were 65 ml and 50 ml, respectively, per 1 m ² of the light-sensitive material. The crossover time is 5 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Unit (g) Mother liquor Replenisher Diethylenetriaminepentaacetic acid 2.0 2.2 1-Hydroxyethylidene-1,1-3.3 3.3 Diphosphonic acid Sodium sulfite 3.9 5.2 Potassium carbonate 37. 5 41.0 Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N-6.1 8.0 (β-hydroxyethyl) amino] aniline sulfate Add water 1000 ml 1000 ml pH 10.05 10.20

(Bleach) Unit (g) Mother liquor Replenisher 1,3-Diaminopropanetetraacetic acid 42.7 g 61 g Ferric ammonium-hydrate Ammonium bromide 25.2 36 Ammonium nitrate 17.5 25 Acetic acid 84 120 Water In addition 1000 ml 1000 ml pH [adjusted with aqueous ammonia] 4.5 4.2

(Fixer) Unit (g) Mother liquor Replenisher Ammonium sulfite 19 20.3 Ammonium thiosulfate aqueous solution 350 ml 375 ml (700 g / liter) Imidazole 5 5.4 Ethylenediaminetetraacetic acid 15 16 Water was added 1000 ml 1000 ml pH [ammonia water , Adjusted with acetic acid] 7.4 8.1

(Stabilizing Solution) Unit (g) Mother Liquor Replenishing Solution N, N′-bis (1,2,4-tri 0.5 0.55 azol-1-ylmethyl) piperazine 1,2,4-triazole 1 0.0 1.1 Ethylenediaminetetraacetic acid 0.04 0.044 Surfactant W-7 0.2 0.22 Water was added to 1000 ml 1000 ml (wash water) was well water.

The same running treatment was carried out by adding the antibacterial agents shown in Table 4 to the stabilizing solution. Sensitometry was performed on the light-sensitive material 201 processed at the end of each running, and the photographic properties were compared. The results obtained are shown in Table 4.

[0069]

[Table 4]

It is understood that when the conventionally known antibacterial agent benztriazole is added, the photographic sensitivity is lowered, whereas the compound of the present invention is preferable because it does not have such adverse effects on photographic properties.

Example 3 (Preservative effect of rinse liquid) Automatic developing machine FNCP-600 manufactured by Fuji Photo Film Co., Ltd.
A running solution was applied to the (rinse specification) by adding a starting solution of the negative treating agent CN-16X. The processing steps are as follows. Treatment process Treatment time Treatment temperature Replenishment amount * (℃) (ml) Color development 3 minutes 15 seconds 38.0 428 Bleach 3 minutes 38.0 140 Fixing 3 minutes 38.0 400 Rinse (1) 45 seconds 38.0 -Rinse (2) 1 min 30 sec 38.0 Stability 45 sec 38.0 570 Dry 120 sec 55 * Replenishment amount per 1 m ² of light-sensitive material Rinse from (2) to (1) It is a countercurrent method. Ion-exchanged water was used as the rinse liquid. A color negative film manufactured by Fuji Film Co., Ltd., SHG-100, was processed at a rate of 20 films a day for 2 weeks while being replenished. At this point, slight turbidity was observed in the rinse liquid tank, and when the automatic developing machine was stopped with the liquid still left for 3 days, a remarkable turbidity was observed. Stain due to turbidity was found on the film surface. The same running treatment was carried out by adding the antibacterial agent of the present invention and the known antibacterial agent B (the same as in Example 1) to the rinse solution. The results obtained are shown in Table 5.

[0072]

[Table 5]

When the known antibacterial agent B is used, there is no problem of spoilage with the conventional replenishing amount, but if the replenishing amount of the rinse liquid is further reduced, the spoilage of the liquid due to spoilage occurs and the film is soiled. The problem arises. On the other hand, when the antibacterial agent of the present invention is used, it is found that extremely good treatment can be performed without spoilage.

[0074]

According to the present invention, it is possible to prevent the stabilizing solution and the rinsing solution from preserving without deteriorating the photographic property.

Claims (7)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one aminoglycoside selected from gentamicin, amikacin, tobramycin, dibekacin, micronomycin, isepamycin, sisomycin, netilmycin and astromycin. Stabilizer. 2. A silver halide color photographic light-sensitive material containing at least one aminoglycoside selected from gentamicin, amikacin, tobramycin, dibekacin, micronomycin, isepamycin, sisomycin, netilmycin and astromycin. Rinse solution. 3. A silver halide color characterized by being treated with a stabilizing solution containing at least one aminoglycoside selected from gentamicin, amikacin, tobramycin, dibekacin, micronomycin, isepamycin, sisomycin, netilmycin and astromycin. Processing method of photographic light-sensitive material. 4. A silver halide color characterized by being treated with a rinse solution containing at least one aminoglycoside selected from gentamicin, amikacin, tobramycin, dibekacin, micronomycin, isepamycin, sisomycin, netilmycin and astromycin. Processing method of photographic light-sensitive material. 5. The stabilizing solution according to claim 1, wherein the stabilizing solution is substantially free of formalin. 6. The method of processing a silver halide color photographic light-sensitive material according to claim 3, wherein the stabilizing solution contains substantially no formalin. 7. A replenishing amount of a color developing solution is 1 m ^{2 of the} light-sensitive material.
7. The amount per 660 ml or less
The processing method described.