JP2811268B2 - Stabilizing solution and rinsing solution for silver halide color photographic light-sensitive material and processing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

The photosensitive material on which an image has been formed is washed with water, rinsed and / or rinsed after desilvering in order to preserve the obtained image.
Alternatively, a stabilization process is performed. The rinsing process is a process of effectively washing out the processing chemicals from the photosensitive material. Rinse treatment is a process called rinse water replenishment, which replenishes water according to the processing amount of photosensitive material, instead of flushing water at a constant flow rate, and is a process in which the amount of water used is reduced. . In this rinsing, a simple water is used. If necessary, an additive for increasing the efficiency of the rinsing, for example, a trace amount of a salt such as sodium sulfate or potassium sulfate, or a trace amount of a chelating agent such as ethylenediaminetetraacetic acid (EDTA) is used. Is also added. The stabilizing process is a processing solution containing an image stabilizer for preventing image deterioration, and includes a stabilizing solution used for a final bath in the processing of a color negative film or a color reversal photosensitive material. In the case of a color reversal photosensitive material, an adjustment stabilizing solution containing an image stabilizer in a processing solution used between the color developing step and the desilvering step, which is called an adjusting solution, has also been proposed. See James, "The Theory of
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 the processing has been promoted. Processing with a large amount of replenisher, which can be treated with a liquid, has been replaced with processing with a small amount of a replenisher. However, if the replenishment amount of the washing, the rinsing liquid or the stabilizing liquid is reduced, these processing liquids stay in the processing tank for a long time, causing a problem of decay of the liquid. The rinsing solution and the stabilizing solution are different from the color developing solution and other processing solutions in that the salt concentration of the solution is low, and in an environment where bacteria and fungi easily grow, the solution is often stained by bacteria or fungi. It causes problems such as turbidity or decomposition of processing chemical components.

[0005] To address these problems, antibacterial agents,
The addition of anti-binders has been proposed. For example, thiazolyl benzimidazole compounds, isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organic tin and organic zinc compounds, acid amide compounds, diazine and triazine compounds, Thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts such as benzalkonium chloride, etc.
Antifungus Agent (J. Antibact. Ant)
ifung. Agents) Vol 1. No.5, p. 207-223 (1
983).

[0006]

However, such a conventional antibacterial agent which is conventionally known to be used in a processing solution for a photosensitive material has a problem that its effect is small unless it is added in a large amount. Furthermore, it has been found that a new problem arises when combined with low replenishment of the color developer, namely the problem of contamination of the color developer by the stabilizing or rinsing solution components. In a cine-type developing machine, the leader bonded to the processed film passes through the final bath together with the film and is dried as it is. In this manner, the leader to which the stable liquid component or the rinse bath component of the final bath is attached is reused without being washed, so that the attached stable liquid component is brought into the developer. Similarly, in a hanger type developing machine, the same phenomenon occurs by adhesion to a film hanger. As a result of the remarkably low replenishment of the color developing solution, the accumulated concentration increases, and as a result, the conventional antibacterial agent contained in the stabilizing solution or the rinsing solution may adversely affect photographic properties such as generation of fog and reduction in sensitivity. understood.

Accordingly, a first object of the present invention is to provide a stabilizing solution, a rinsing solution, and a processing method using the same, which do not cause spoilage even by low replenishment and 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 effect on photographic properties (for example, decompose an image stabilizer) and prevent decay. It is in. Further, a third object of the present invention is to provide a stabilizing solution, a rinsing solution and a stabilizing solution which are brought into a color developing solution and which do not adversely affect photographic properties such as generation of fog and a decrease in sensitivity even when the color developing solution is replenished at a low level. And a processing method using the same.

[0008]

Means for Solving the Problems The object of the present invention is to include at least one of gentamicins and aminoglycosides which are amikacins (hereinafter referred to as amicoglycosides of the present invention). The problem was solved by a rinsing solution, a stabilizing solution and a method for processing a silver halide color photographic light-sensitive material using the same.

Hereinafter, the present invention will be described in detail. The rinsing liquid in the present invention refers to a processing liquid for performing a so-called rinsing water washing in which an amount corresponding to the processing amount of the photosensitive material is replenished, instead of flushing the washing water at a constant flow rate. The rinsing liquid basically uses only water, and if necessary, additives such as a salt such as a small amount of sodium sulfate or potassium sulfate, or a small amount of an additive such as ethylenediaminetetraacetic acid (EDTA) to increase the washing efficiency. A suitable chelating agent can be added. Further, a surfactant may be contained in order to prevent water droplet unevenness during drying. The stabilizer in the present invention refers to a processing solution and a replenisher thereof for preventing deterioration of a color image such as a color negative film or a color reversal film, and in addition to a stabilizer used as a final bath after the desilvering step, in particular. And an adjustment stabilizer such as a color reversal film.

The amicoglycosides of the present invention will be described. The amicoglycosides of the present invention are those known as preservatives. For example, gentamicins are disclosed in U.S. Patent Nos. 3,091,572 and 3,136,70.
No. 4, and with respect to amikacin, reference can be made to U.S. Pat. No. 3,781,268. Specific examples of gentamicins are shown below.

[0011] Compound No. 1 gentamicin A ₂ 2 gentamicin A 3 gentamicin A ₁ 4 gentamicin B 5 gentamicin X ₂ 6 anti-biotic JI-20A 7 gentamicin B ₁ 8 anti-biotic G418 9 Anti-biotic JI-20B 10 gentamycin 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.
See also the Merck Index for these properties.
(TheMerck Index) 11th edition (1989) MERCK & Co., INC.
It is described in. Among the aminoglycosides of the present invention, gentamicins are particularly preferred. The aminoglycosides of the present invention may be added to a stabilizing solution or a rinsing solution at the time of use, or may be previously contained in a concentrated stabilizing solution. The amount of addition is 1 ppm to 100 ppm, preferably 3 to 5 ppm, in a stable solution or a rinsing solution as a final use solution.
It is 0 ppm. In many cases, the stabilizer is supplied as a concentrated stabilizer and diluted at the point of use. The concentration of the compound of the present invention in the concentrated stable liquid is 30 ppm to 10000 pp.
m, and preferably 300 to 3000 ppm.

In particular, it has also been found that when the aminoglycosides of the present invention are contained in a stabilizer that is substantially free of formalin, the bactericidal effect of the solution is maintained for a long time, and more favorable results are obtained. That is, the stabilizer of the present invention can contain any image stabilizer, but in the present invention, it contains substantially no formalin, and the effect is obtained when an image stabilizer other than formalin is used. Large and preferred.
In the present invention, substantially not containing formalin means that the concentration of free formaldehyde in the liquid is 0.01% or less, and more preferably 0.005% or less.
% Or less.

As an image stabilizer other than formalin,
Any known one can be used. As an image stabilizer other than formalin, JP-A-63-244036
Discloses a hexamethylenetetramine-based compound. Many N-methylol compounds having a specific structure have been proposed. For example, U.S. Pat.
487,569 and 2,629,660, N-methylol compounds of melamine compounds, U.S. Pat.
U.S. Pat. No. 9,435, Urea of 2-oxapropylene urea
Methylol compounds, U.S. Pat. No. 2,487,446;
JP-B-45-8506, N-methylol compound of a thiourea compound, U.S. Pat. No. 2,579,436, N-methylol compound of a hydantoin compound of British Patent 684,540, and British Patent 908,136. N-methylol compounds of cyanodiamide compounds, U.S. Pat.
801-322, N-methylol compound of guanidine compound disclosed in JP-A-61-35447, British Patent No. 1,39
No. 2,134, morpholine and biuret compound N-methylol compound, and JP-A-2-153348, pyrrole, pyrrolidine, methylamine, glycine and ethylcarbamate N-methylol compounds are known.

Particularly preferred N-methylols include pyrazole, 1,2,2 described in JP-A-4-270344.
An N-methylol compound of 4-triazole may be mentioned. Also, regarding the use of these compounds,
U.S. Pat. Nos. 4,786,583 and 4,859,5
No. 74, No. 4,921,779, European Patent No. 3
Nos. 45,172 and 395,442. An azolylmethylamine compound is also effective. In particular, the azolylmethylamine compound described in EP-A-050409A2 has no generation of free formaldehyde gas, has a high dye image stabilizing effect, and is particularly preferable. 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. Hereinafter, specific examples of formalin substitutes are shown, but the present invention is not limited to these.

[0016]

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[0017]

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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 is preferably 0.001 to 0.01 mol.
More preferably, it is 1 to 0.05 mol. When the stabilizing solution or the rinsing solution of the present invention is provided as a final bath for the treatment, it is preferable to add a surfactant to prevent drying unevenness of the film. Any surfactant can be used. For example, polyethylene glycol type nonionic surfactant, polyglycidol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type Anionic surfactant, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric interface 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 stain and water-spot unevenness. As the alkylphenol, octylphenol, nonylphenol, dodecylphenol and dinonylphenol are particularly preferable. The number of moles of ethylene oxide added is particularly preferably 8 to 14, and the number of moles of glycidol is particularly preferably 6 to 13. It is also preferable to use a silicon surfactant having a high defoaming effect. Examples of preferred surfactants are shown below, but the present invention is not limited thereto.

[0019]

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The amount of the surfactant is 0.005 g to 3 g, preferably 0.02 g to 3 g per liter of the stabilizing solution.
0.3 g. The stabilizer of the present invention may further contain an organic acid or a pH buffer. In addition, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, a fluorescent brightener, a hardener, or an alkanolamine described in US Pat. No. 4,786,583 can be used.

It is preferable that the stabilizer of the present invention 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, diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent No. 345172A1. The pH of the stabilizer of the present invention is usually used in the range of 4.0 to 10, preferably 5.0 to 9.0, more preferably 6.0.
5 to 8.6.

The composition of the stabilizer of the present invention can be maintained by supplying a certain amount of replenisher according to the treatment.
The composition of the replenisher is set so as to compensate for the consumption of the active ingredient due to the treatment, the dilution by bringing in the liquid from the previous bath, and the like.
Normally, this replenisher is supplied at a concentration of 10 to 200 times that of the stable replenisher, and is supplied by dividing into a plurality of concentrates, and the plurality of concentrated compositions are mixed and diluted to obtain a replenisher. You may do so. The concentration is preferably 15 to 300 times.
Times, more preferably 50 times to 150 times. In the case of continuous processing using the stable replenisher of the present invention, the processing is preferably carried out while replenishing the photosensitive material at a rate of 100 to 1700 ml per 1 m ² , more preferably 200 to 650 ml, particularly preferably 200 to 580 ml. The stabilizer of the present invention is generally used in the final step following the ordinary color development and desilvering steps, but is not necessarily limited thereto. Regarding the processing formula such as the color developing step, the desilvering step, and the washing step, and the processing steps, refer to
466545.

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, for example, 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. Of these, particularly preferred is 2-methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino] aniline. Further, these p-phenylenediamine derivatives are sulfates,
Salts such as hydrochloride, sulfite and p-toluenesulfonate may be used. The amount of the aromatic primary amine color developing agent used is 0.001 to 0.
A concentration of 1 mol is preferred, more preferably 0.01 to
0.06 molar concentration.

In the color developer, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as potassium bisulfite, sodium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. The preferred amount of the preservative is 0.5 to 10 g, more preferably 1 to 5 g, per liter of the color developing solution. Various hydroxylamines (for example, JP-A-63-163) can be used as compounds for directly preserving the aromatic primary amine color developing agent.
Compounds described in Nos. 5341 and 63-106655,
Among them, compounds having a sulfo group or a carboxy group are preferred. ), 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 JP-A-63-44656, and / or various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254 and JP-A-63-24
Nos. 1647, 63-146040, 63-278
Monoamines described in No. 41 and No. 63-25654, No. 63-30845, No. 63-14640,
Diamines described in JP-A-63-43139 and the like;
Nos. 21647, 63-26655 and 63-4
No. 4655, polyamines described in JP-A-63-53551, alcohols described in JP-A-63-43140 and JP-A-63-53549, and an alcohol described in JP-A-63-53549.
Oximes described in No. 56654 and 63-2394
It is preferable to use the tertiary amines described in No. 47.

Other preservatives include JP-A-57-441.
Various metals described in JP-A Nos. 48 and 57-53749, salicylic acids described in JP-A-59-180588,
Alkanolamines described in JP-A-54-3582,
Polyethylene imines described in JP-A-56-94349 and aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0. The color developing solution may further contain a compound of a known developing component. 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), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The amount of the buffer added to the color developing solution is preferably 0.1 mol / L or more, and particularly preferably 0.1 to 0.1 mol / L.
Particularly preferred is 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing precipitation of calcium and magnesium, or for improving the stability of the color developing solution. As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Representative examples thereof include 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- Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid and the like. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block metal ions in the color developing solution.
It is about 0.1 g to 10 g per liter.

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

In the present invention, if necessary,
Optional antifoggants can be added. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-
Nitrogen-containing compounds such as nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine Heterocyclic compounds can be mentioned as typical examples.

The processing temperature of the color developing solution in the present invention is
The temperature 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, more preferably 1 minute to 2 minutes 30 seconds. Departure
In the light, the replenishment amount of the color developing solution is 1 m^TwoThis
It is 85-120 ml, but the effect of the antibacterial agent of the present invention.
Means that the replenishment rate is 300-660 ml / m ^Two, Especially 30
0-430m^TwoIn particular. The phosphorus of the present invention
Solution, stabilizing solution and processing using it
Adaptable for, but especially color negative photography
Applicable to photographic materials or color reversal photographic materials
Thus, the effect is greatly exhibited. These photosensitive materials
Regarding the above, JP-A-3-46654 and 2-854
No. 2-90151, No. 4-270344, Europe
It is described in Patent Publication No. 0504609A and the like. Shooting
Color negative photographic light-sensitive material for shadow or color reversal photographic feeling
As silver halide used for optical materials, silver iodide is used.
Silver iodobromide containing 0.2 to 20 mol% is preferred.

[0031]

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

This was designated as Stable Replenisher 1, and Stable Replenishers 2 to 7 having the same composition except that the preservative of the present invention shown in Table 1 was added thereto were prepared. For comparison, see Japanese Unexamined Patent Publication No.
Bactericidal agent A described in 1-35446 and JP-A-57-85
Stable replenishers 8 to 13 to which the antibacterial agent B described in 41 were added were prepared.

[0033]

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An automatic processor FP manufactured by Fuji Photo Film Co., Ltd.
At -350, a starting solution of the processing agent CN-16Q manufactured by the company was applied. However, the above-mentioned blank stable replenisher was applied to the stabilizing bath. In the same manner, the color negative film and SHG-100 were replenished at a rate of 20 a day for 2 weeks while replenishing to obtain a running liquid. 10 ml of this running solution was added to 100 ml of each of the above stabilizing replenishers, placed in a 30 ° C. air bath, left standing, sampled on the third day, the first week and the second week, and 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 determination level, and Table 2 shows the test results.

[0035]

[Table 1]

[0036]

[Table 2]

In the case of a blank having no antibacterial agent, the proliferation of bacteria is remarkable, and the image stabilizer is decomposed. On the other hand, when a known antibacterial agent is added, the proliferation of bacteria is suppressed. It requires high addition concentrations and the effect is incomplete. On the other hand, when the compound according to the present invention is added, a sufficient antibacterial effect can be obtained with a small amount, there is no generation of null in the liquid, and no decomposition of the image stabilizer occurs.

Example 2 (Contamination test of developer) On a cellulose triacetate film support having an undercoat,
A color negative film 201 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 for silver halide and colloidal silver.
/ M ² units, for couplers, additives and gelatin, the amount in g / m ² units, and for sensitizing dyes, the amount per mole of silver halide in the same layer. Indicated by 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 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 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 6th 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 Eighth layer: Medium-speed green-sensitive 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 × 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 ^-3 ExM-6 5.0 × 10 ^-3 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-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-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 14th 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 16th layer: High-sensitivity blue-sensitive emulsion layer 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 × 10 ^-2 HBS-2 1.0 × 10 ^-2

18th layer: 2nd protective layer Fine grain 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 WA-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00 In addition to the above, the sample thus prepared includes 1,2-benzisothiazolin-3-one (based on gelatin). Average 20
0 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm). Further, B-4 to B-6, WA-2, WA-3, F-1 to F-1
5, contains iron salts, lead salts, gold salts, platinum salts, iridium salts, rhodium salts and palladium salts.

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[Table 3]

In Table 3, (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 and sodium thiocyanate described in each photosensitive layer according to the examples of JP-A-3-237450. I have. (3) For preparing 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 using a high-pressure electron microscope.

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The color negative film 201 thus prepared was slit into a width of 35 mm and used for an experiment.
The processing was carried out while replenishing using a small cine-type automatic developing machine. Before and after the color negative film 201, a leader having a length of 10% of the film was joined. After processing, the leader was removed from the film and reused without washing. The processing was continued until the liquid in the developer tank was replaced twice.

Processing step Step Processing time Processing temperature Replenishment amount * Tank capacity (° C.) (ml) (liter) Color development 3 minutes 15 seconds 38.0 428 2 Bleaching 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 Washing is a countercurrent method from (2) to (1). The amount of the developer 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 m ² of the light-sensitive material. The crossover time is 5 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) Unit (g) Mother liquor Replenisher diethylenetriaminepentaacetic acid 2.0 2.2 1-hydroxyethylidene-1,1-3.3 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

(Bleaching solution) Unit (g) Mother liquor Replenisher 1,3-diaminopropanetetraacetic acid 42.7 g 61 g Ferric ammonium-hydrate ammonium bromide 25.236 Ammonium nitrate 17.5 25 Acetic acid 84 120 Water was added. In addition, 1000 ml 1000 ml pH [adjusted with aqueous ammonia] 4.5 4.2

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

(Stabilizing solution) Unit (g) Mother liquor Replenisher N, N′-bis (1,2,4-tri 0.5 0.55 azole-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, and 1000 ml 1000 ml (washing water) used well water.

A similar running treatment was carried out by adding the antibacterial agent shown in Table 4 to the stabilizing solution. Sensitometry was performed on the processed photosensitive material 201 at the end of each run to compare photographic properties. Table 4 shows the obtained results.

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[Table 4]

It can be seen that when a conventionally known antibacterial agent, benzotriazole, is added, the photographic sensitivity is reduced, whereas the compound of the present invention is preferable because it has no such adverse effect on photographic properties.

Example 3 (Preservative Effect of Rinse Solution) Automatic Developing Machine FNCP-600 manufactured by Fuji Photo Film Co., Ltd.
(Rinse specification) was applied with a starting solution of the same negative treating agent CN-16X, and a running test was conducted. The processing steps are as follows. Processing step Step Processing time Processing temperature Replenishment rate * (° C) (ml) Color development 3 minutes 15 seconds 38.0 428 Bleaching 3 minutes 38.0 140 Fixing 3 minutes 38.0 400 Rinse (1) 45 seconds 38.0 - rinse (2) stable 45 seconds 38.0 570 drying 120 seconds 55 * replenishment rate according to 1 minute 30 seconds 38.0 table 5 the amount rinsing per photosensitive material 1 m ² from (2) to (1) It is a countercurrent method. Ion exchange water was used as the rinsing liquid. The color negative film, SHG-100, manufactured by Fuji Film Co., Ltd. was treated at a rate of 20 a day for 2 weeks while replenishing. At this time, slight turbidity was observed in the rinsing liquid tank. Further, when the automatic developing machine was stopped with the liquid remaining and left for 3 days, significant generation of dust was observed. Dirt due to turbidity was observed on the film surface. The same running treatment was carried out by adding the bactericide of the present invention and a known bactericide B (the same as in Example 1) to the rinse solution. Table 5 shows the obtained results.

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[Table 5]

When the known antibacterial agent B is used, there is no problem of spoilage if the conventional replenishment amount is used. However, if the replenishment amount of the rinse solution is further reduced, the liquid will be stained due to spoilage and the film will be soiled. Problems arise. On the other hand, when the antibacterial agent of the present invention was used, it was found that extremely good treatment could be performed without causing rot.

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According to the present invention, preservation of a stabilizing solution and a rinsing solution can be achieved without deteriorating photographic properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 11/00 501 G03C 7/407 G03C 7/44

Claims (7)

(57) [Claims] 1. A stabilizer for silver halide color photographic material which comprises at least one gentamicin acids or amikacin. 2. A rinsing solution for a silver halide color photographic light-sensitive material, comprising a gentamicin or amikacin. 3. A method for processing a silver halide color photographic material, which comprises treatment with a stabilizing solution containing at least one gentamicin acids or amikacin. 4. A method for processing a silver halide color photographic material which comprises treating with a rinse liquid containing at least one gentamicin acids or amikacin. 5. The stabilizer according to claim 1, wherein the stabilizer is substantially free of formalin. 6. The method for processing a silver halide color photographic light-sensitive material according to claim 3, wherein said stabilizer contains substantially no formalin. 7. The replenishment amount of the color developing solution is 1 m ^{2 of the} photosensitive material.
7. The volume per bottle is 660 ml or less.
The processing method described.