JPH077202B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, it relates to a processing method in which the stability of a color developing solution is improved and the stain and image stability of a processed color light-sensitive material are remarkably improved.

(Prior Art) In recent years, in the process of automatically and continuously developing general color photographic processing, environmental conservation and reduction of silver resources,
Recovery is regarded as important, and measures to prevent pollution, efficiently recover silver, reduce the amount of washing water or stabilizing solution, and reuse are under consideration.

For example, in order to greatly reduce the amount of wash water or stabilizing solution replenisher, a multi-stage countercurrent method has been considered in which the baths for the washing process or stabilizing process are provided in multiple tanks and the replenisher is countercurrently replenished. ing.

This makes it possible to reduce the amount of waste liquid, significantly reduce pollution load, and easily reduce the amount of water used and reuse it.

Japanese Unexamined Patent Publication No. 57-8543 discloses a treatment method in which after the fixing treatment, a stabilizing treatment is carried out by replenishing the stabilizing solution by a multistage countercurrent system consisting of multiple tanks. In this treatment method, the replenishment amount of the stabilizing solution is as small as 3 to 50 times the carry-in amount from the previous bath, so that the amount of water used can be greatly reduced,
It is an advantageous treatment method for environmental protection and water resource issues that have been emphasized in recent years.

However, with such a treatment method of simply reducing the amount of washing water or the amount of stable liquid by adopting a multi-stage countercurrent method,
Processing a color photographic light-sensitive material has a drawback that stain after processing is extremely deteriorated. Such stains are particularly easily visually perceived in the reflective light-sensitive material, and are inevitably a problem in practical use.

This stain can be removed by rewashing, or
Due to the fact that it does not occur when the washing time is sufficiently extended, or it does not occur when the color developer is replaced with a fresh solution, it occurs because the oxidizing component of the color developer adheres to the photosensitive material and is not washed sufficiently. It is supposed to do.

Conventionally, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as preservatives, JP-A-52-49828, 59-160142,
No. 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat.No. 3,746,544, hydroxycarbonyl compounds described in U.S. Patent No. 3,625,503 and British Patent No. 1306176, JP-A Nos. 52-143020 and 53-89425. [Alpha] -aminocarbonyl compounds, alkanolamines described in JP-A-54-3532, metal salts described in JP-A-57-44148 and 57-53749, and the like. Further, as the chelating agent, aminopolycarboxylic acids described in JP-B-48-030496 and 44-30232, JP-A-56-97347, JP-B-56347
-39359 and West German Patent 2227639, organic phosphonic acids, JP-A-52-102726, JP-A-53-42730, and JP-A-54-12112.
No. 7, No. 55-126241 and No. 55-65956, and the like, phosphonocarboxylic acids described in JP-A Nos. 58-195845 and 58.
Compounds described in, for example, No. -203440 and Japanese Patent Publication No. 53-40900 can be mentioned.

However, even if these compounds are used, sufficient preservative performance is not obtained, and when the replenishment amount is reduced in the washing treatment or the stabilizing treatment as in the present invention, the processed color light-sensitive material is An increase in stain was observed.

Further, it is already known that benzyl alcohol is used in a color developing solution for improving color development, but benzyl alcohol has poor solubility in the processing solution, and it takes time to prepare the processing solution. In addition, there are problems such as generation of tar due to deterioration of the processing liquid with time, or occurrence of color restoration failure and deterioration of image storability after processing in photographic properties.

With respect to the above problems, for example, as a technique for improving the stability of the developing solution by adding the compound of the general formula (I) according to the present invention to the color developing solution, Japanese Patent Publication No. 53-12381. It is described in. However, as described in the patent examples, although some effects are recognized in the presence of benzyl alcohol, when the replenishment amount in the washing process or the stabilizing process is reduced as described in the present invention, the color photographic material is reduced. An increase in the stain (particularly yellow stain) was observed.

(Object of the Present Invention) Therefore, the first object of the present invention is to provide a stable processing solution in which the deterioration of the color developing solution with time is prevented.
It is a second object of the present invention to provide a processing method which is a multi-stage countercurrent method with a low replenishment amount and which is capable of obtaining stable photographic performance with less stain after processing in a method of washing or stabilizing. .

(Structure of the Invention) The object of the present invention was achieved by the method described below.
That is, in a processing method in which a silver halide color photographic light-sensitive material is subjected to color development processing, followed by desilvering processing, water washing processing or stabilization processing, the color development processing solution contains substantially no benzyl alcohol, and A halogen containing at least one kind of the compound represented by the general formula [I] and comprising a multiplicity of tanks for the washing treatment step or the stabilization treatment step, and the replenishing amount thereof when replenishing in a multistage countercurrent system. According to the method for processing a silver halide color photographic light-sensitive material, the amount per unit area of the silver halide color photographic light-sensitive material is 3 to 50 times the carry-in amount from the previous bath.

General formula [I] (M may be the same or different and represents a hydrogen atom, an alkali metal ion or an ammonium ion. When M is a cation having a valence of 2 or more, it represents 1 / n of these cations depending on the valence number n. The amount of the compound of the general formula [I] added is 0.001 g to 30 g, preferably 0.005 g to 10 g, and more preferably 0.01 g to 5 g per color developing solution. Specific examples of the compound of general formula [I] include 1,2-cyclohexanediamine-N, N, N ', N'.
-Tetraacetic acid, sodium salt, potassium salt, lithium salt, ammonium salt and the like.

It is already known that the compound of the present invention is contained in a color developing solution for processing, but in the processing in which the replenishing amount is decreased in the washing process or the stabilizing process, the above compound is not simply used. However, the stain of the processed color light-sensitive material could not be sufficiently suppressed.

The present inventors have found that the cause of this stain is due to the adhesion of the oxidizing component of the color developing solution, and that benzyl alcohol, which is the developing solution component, is involved in the production or adhesion thereof.

As described above, the developer of the present invention in which the compound generated by the formula (I) is contained in the developing solution in which the stain generated in the process of reducing the replenishing amount of the washing process or the stabilizing process does not substantially contain benzyl alcohol. It can be said that it was difficult to infer that the combination can be effectively suppressed only in the combination.

In the present invention, substantially free of benzyl alcohol means that the concentration of benzal alcohol in the color developer is 2 ml /
It is below, preferably 0.5 ml / or less, more preferably not containing at all.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- (Β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylene Diamine D-9 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

The color developer used in the present invention may contain hydroxylamines as is well known.

Hydroxylamines are more commonly used in the form of water-soluble acid salts, although they can be used in the free amine form in color developers. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates and others. The hydroxylamines may be substituted or unsubstituted,
The nitrogen atom of the hydroxylamines may be replaced by an alkyl group.

Addition amount of hydroxylamine is 0g per 1 color developer
-10g, preferably 0-5g. If the stability of the color developing solution is maintained, it is preferable that the addition amount is small.

As a preservative, sodium sulfite, potassium sulfite,
Sulfite salts such as sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts may be contained. The addition amount of these is
The amount is 0 g to 20 g / preferably 0 g to 5 g /, and the smaller amount is preferable if the stability of the color developing solution is maintained.

Other preservatives are US Patent 3615503 and UK Patent 1
Hydroxyacetones described in 306176, JP-A-52-1430
No. 20 and No. 53-89425 described α-aminocarbonyl compounds, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727, 52
Hydroxamic acids described in No. 27638. 59-160141 described α, α'-dicarbonyl compounds, 59-180588 described salicylic acids, 54-3532 described alkanolaminos, 56-94349 described poly (alkyleneimines, Gluconic acid derivatives described in U.S. Pat. No. 56-75647, U.S. Pat.
746544 and the aromatic polyhydroxy compounds described in JP-A-56-47038 and JP-A-59-160142.
Two or more kinds of these preservatives may be used in combination, if necessary.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy salt Phenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they are effective for photographic performance. It is particularly preferable to use these buffers because they have no ill effects (fogging, etc.) and have an advantage that they are inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, 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. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol / or more, and particularly 0.1 mol / to 0.4 mol /
Is particularly preferable.

In addition, various chelating agents other than the compound of the general formula [I] can be used as a precipitation inhibitor of calcium or magnesium in the color developing solution or for improving the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, for example, aminopolycarboxylic acids described in JP-B-48-030496 and 44-30232, JP-A-56-97347, JP-B-56-39359 and West German patent 2227639. Organic phosphonic acids of JP-A Nos. 52-102726, 53-42730, 54-121127 and 5
Examples include phosphonocarboxylic acids described in 5-126241 and 55-65956, and compounds described in JP-A-58-195845, 58-203440, and JP-B-53-40900. . Specific examples are shown below, but the present invention is not limited thereto.

・ Nitrilotriacetic acid ・ Diethylenetriamine pentaacetic acid ・ Triethylenetetramine hexaacetic acid ・ N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1,3-Diamino-2 -Propanol-4acetic acid-Ethylenediaminetetraacetic acid-Nitrilotripropionic acid-1,2-Diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol etherdiaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxyphenylacetic acid-2- Phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These chelating agents are required Two or more kinds may be used together depending on the case.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

Any development accelerator can be added to the color developing solution if necessary. However, it contains substantially no benzyl alcohol,
The amount of addition is 0.5 ml / or less per one color developer, and preferably it is not contained at all. Other development accelerators include JP-B-37-16088, 37-5987, and 38-7826.
No. 44-12380, No. 45-9019 and U.S. Pat.
Compounds represented by JP-A-52-49
Nos. 829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30
074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in US Pat. Nos. 2610122 and 4119462, US Pat. Nos. 2494903 and 3128182. , 4230796, and 3253919
No. 4, Japanese Patent Publication No. 41-11431, U.S. Pat.
Amine compounds described in No. 6 and No. 3582346, etc.
37-16088, 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publications 41-11431, 42-23883, and U.S. Pat.
No. 1 and other polyalkylene oxides
-Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

In the present invention, an optional antifoggant can be added to the color developer, if necessary. As the antifoggant, alkali metal halides such as potassium bromide, sodium bromide and potassium iodide, and organic antifoggants can be used.
Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Niazolylmethyl-benzimidazole, nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and further thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color light-sensitive material during processing and accumulated in the color developing solution.

The color developer of the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,
2'-Disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / preferably 0.1 g to 2 g /.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30-40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the replenishment amount is, the more preferable it is 20 to 600 ml, preferably 50 to 300 ml per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

In the present invention, desilvering processing is carried out after color development processing. The desilvering process is mainly separated into a bleaching process and a fixing process, but a bleach-fixing process which is performed at the same time can be used. Typical examples of the desilvering process include bleach-fixing, bleach-fixing, bleach-bleach-fixing, fixing-bleach-fixing, bleach-fixing-fixing, etc., and a desilvering accelerator before each of these baths. The baths may be provided, and each of these baths may be divided into two or more to accelerate the desilvering rate or reduce the replenishment amount.

In the bleaching bath and bleach-fixing bath used in the present invention, bleaching agents such as red blood salt, dichromate, persulfate, inorganic ferric salt,
It can be used by arbitrarily selecting it from known ones such as ferric salts of organic acids, but there is little water pollution and metal corrosion,
It is particularly preferable to use a ferric aminopolycarboxylic acid complex salt having good stability. Two or more bleaching agents can be used in combination. The bleaching bath and the bleach-fixing bath may have different bleaching agents. For example, the bleaching bath may contain iron chloride and the bleach-fixing bath may contain ferric aminopolycarboxylic acid complex salt. The ferric aminopolycarboxylic acid complex salt is a complex of ferric ion and aminopolycarboxylic acid or a salt thereof.

As typical examples of these aminopolycarboxylic acids and salts thereof, A-1 ethylenediaminetetraacetic acid, A-2 diethylenetriaminepentaacetic acid, A-3 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid, A-4 1,3-diaminopropanetetraacetic acid, A-5 triethylenetetramine hexaacetic acid, A-6 propylenediaminetetraacetic acid, A-7 nitrilotriacetic acid, A- 8 nitrilotripropionic acid, A-9 cyclohexanediaminetetraacetic acid, A-10 1,3-diamino-2-propanoltetraacetic acid, A-11 methyliminodiacetic acid, A-12 iminodiacetic acid, A-13 hydroxyiminodiacetic acid, A-14 dihydroxyethylglycine ethyl ether diamine tetraacetic acid, A-15 glycol ether diamine tetraacetic acid, A-16 ethylene diamine tetrapropionic acid, A-17 ethylene diamine dipropion acetic acid, A-18 phenylenediamine tetraacetic acid, A-19 2 -Phosphonobutane-1,2,4-triacetic acid, A-20 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, A-21 ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, A-22 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid, A-23 1- Hydroxyethylidene-1,1-diphosphonic acid, etc. may be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these A-
1, A-2, A-4, A-9, A-11, and A-15 are preferred because of their high bleaching power.

These bleaching agents are preferably used in an amount of 0.05 mol to 0.5 mol, more preferably 0.1 mol to 0.4 mol, per 1 working solution.

The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric salt such as ferric sulfate or ferric chloride.
A ferric ion complex salt may be formed in a solution by using ferric nitrate, ferric ammonium sulfate, ferric phosphate and the like and an aminopolycarboxylic acid. 1 when used in the form of a complex salt
Different kinds of complex salts may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used. Further, in any case, the aminopolycarboxylic acid may be used in an excess amount over forming the ferric ion complex salt.

Further, the bleaching solution or bleach-fixing solution containing the ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

The fixing agents used in the present invention are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6. A thioether compound such as dithia-1,8-octanediol and a water-soluble silver halide solubilizer such as thioureas, and these may be used alone or in admixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. Use liquid 1
The amount of the fixing agent is preferably 0.3 to 2 mol, and more preferably 0.5 to 1.0 mol.

The pH range of the desilvering process bath in the present invention is preferably from 4 to 8.5, more preferably from 5 to 8. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

If necessary, various bleaching accelerators can be used in the bleaching bath, bleach-fixing bath or its pre-bath of the present invention. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
2,059,988, JP-A-53-32736, JP-A-53-57831,
No. 37418, No. 53-65732, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc., and compounds having a mercapto group or a disulphide group; JP-A No. 50-140129. Thiazolidine derivatives as described; JP-B-45-8506, JP-A-52-20832, 53-3
2735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide described in JP-A-58-16235; polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-B-45-88836; Other JP-A-49-42434, JP-A-49-42434
9-59644, 53-94927, 54-35727, 55-26
Compounds and iodine described in No. 506 and No. 58-163940,
Bromide can also be used. Among them, a compound having a mercapto group or a disulphide group is preferable from the viewpoint of having a large accelerating effect, and particularly, U.S. Patent No. 3,893,858 and West German Patent No.
The compounds described in 1,290,812 and JP-A-53-95630 are preferred.

In addition, in each desilvering bath of the present invention, bromide (eg potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg ammonium iodide) Can be included. Boric acid, if necessary
Borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
It is possible to add one or more kinds of inorganic acids and organic acids having a pH buffering ability and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

In the bleach-fixing solution and fixing bath of the present invention, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, etc. ), A metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound.
These compounds are approximately 0.02 to 0.30 in terms of sulfite ion.
It is preferable that it is contained per mol, more preferably 0.
It is 10 to 0.20 mol /.

Other preservatives that can be used in the present invention include hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds (eg, acetaldehyde sodium bisulfite).
And so on.

Further, each desilvering bath may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The processing temperature of this desilvering bath is 10 ° to 50 ° C, preferably 20 ° to 40 ° C.
Is. The replenishing amount is ²⁰ ml to 2000 ml, preferably 30 ml to 1500 ml, per 1 m ² of the light-sensitive material.

After the desilvering process (bleach-fixing or fixing), washing with water and / or
Alternatively, processing such as stabilization is performed. Various compounds can be used for various purposes in the washing and stabilizing steps. For example, it is known to add a bactericidal agent or a fungicide to prevent the generation of various bacteria, molds and algae. For example, Journal of Antibacterial and Antifungal Ages (J.Antiba
ct.Antifung.Agents) vol.11, No.5, p207-223 (198
Compounds described in 3) and Hiroshi Horiguchi “Chemistry of antibacterial and antifungal”
Or the compounds described in JP-A-57-8543 and JP-A-57-8543.
57-58143, JP-A-57-97530, JP-A-58-105145, JP-A-58-134636, JP-A-59-91440, JP-A-59-126533,
JP-A-59-184344, JP-A-59-185336, JP-A-60-2397
50, JP-A-60-239751, JP-A-60-247241, JP-A-60-
260952, JP-A-61-2149, JP-A-61-28947, JP-A-61
-28945, Japanese Patent Application No. 59-158475, Japanese Patent Application No. 60-105487, and the method of using the compounds can be applied.

In particular, isothiazolone derivatives (2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-
Isothiazolin-3-one etc.), sulfanilamide derivative (sulfanilamide etc.), and benzotriazole derivative (benzotriazole, 5-methyl-benzotriazole, 5-chloro-benzothiazole etc.)
Is useful.

It is known to add various chelating agents for the purpose of improving the image stability after processing. For example, inorganic phosphoric acid, organic carboxylic acid, aminopolycarboxylic acid, and organic phosphonic acid are useful and are disclosed in JP-A-57-8543 and JP-A-57-197540.
JP-A-58-14834, JP-A-58-134636, JP-A-5
9-126533, JP-A-59-184343, JP-A-59-184344
JP-A-59-184345, JP-A-59-185336, JP-A-SHO
60-135942, JP-A-60-238832, JP-A-60-239748
JP-A-60-239749, JP-A-60-239750, JP-A-60-239750
60-239751, JP-A-60-242458, JP-A-60-262161
No. 61-4747, 61-4050, 61-4050, 61-
4051, JP 61-4052, JP 61-4053, JP
The compounds and methods of use described in JP-A No. 61-4054, JP-A No. 61-28942, and JP-A No. 61-28945 can be applied.

In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene 1,
1'-Diphosphonic acid and ethylenediaminetetramethylphosphonic acid are useful.

A metal compound may be used in combination with these chelating agents. For example, a bismuth compound (JP-A-58-134636)
No.), Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Ti, Sn,
Zn, Zr compounds (JP-A-59-184344), Mg, Al, Sr compounds (JP-A-59-185336) and the like, particularly Bi, Ca, Mg,
Al is useful.

Further, in order to effectively promote washing with water, a surfactant is used (JP-A-57-197540) and a method of contacting with an ion-exchange resin for the purpose of removing a component which has an adverse effect (JP-A-57-197540). 66-220345), a method of reverse osmosis treatment (JP-A-60-241053), activated carbon, clay material, polyamide polymer compound, polyurethane polymer compound, phenol resin, epoxy resin, polymer having hydrazide group Compound, polymer compound containing polytetrafluoroethylene, method of contacting with monovalent or polyhydric alcohol methacrylic acid monoester-polyhydric alcohol methacrylic acid polyester copolymer (JP-A-60-263151), electrodialysis A treatment method (Japanese Patent Laid-Open No. 61-28949) can be applied.

Further, it can be applied as a method for preventing the generation of bacteria and mold such as a method of irradiating ultraviolet rays or passing a magnetic field. Further, in the case of continuously performing the treatment, JP-A-60-233651 and 60-235133.
No. 60, No. 26-39441, No. 61-4048, No. 61-4049, No.
61-4055, 61-4056, 61-4057, 61-4058
No. 61-4060 can be applied.

In addition to the above-mentioned additives, a fluorescent whitening agent, a hardener, etc. may be added to the washing and stabilizing baths.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

As the various additives, the same or different target compounds may be used in combination of two or more depending on the purpose. From the viewpoint of the physical properties of the emulsion film of the processed light-sensitive material (such as stickiness), the addition amount is preferably the minimum amount necessary to achieve the purpose.

It is necessary to reduce the amount of replenisher by using a multi-stage countercurrent flow of two or more tanks in the washing or stabilizing process. The replenisher amount is 0.5 with respect to the carry-in amount of the front bath per unit area of the light-sensitive material.
˜50 times, more preferably 3 to 30 times.

The washing or stabilization treatment time of the present invention depends on the type of sensitive material,
Depending on the treatment conditions, it is 20 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.

The washing or stabilization treatment temperature of the present invention is 20 to 45 ° C, preferably 25 to 40 ° C, and more preferably 30 to 38 ° C.

In order to enhance the effect of washing out components in the film in washing or stabilizing treatment, it is preferable to circulate and stir the liquid,
In particular, a method in which the liquid flow is strong on the emulsion film surface of the light-sensitive material (eg, gas stirring, liquid spraying, etc.) is preferable.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen agitation, air agitation and the like may be provided in each treatment bath.

The typical processing steps used in the present invention are shown below.
It is not limited to these.

1) Color development-bleach-fix-wash-stable-dry 2) Color development-bleach-fix-stable-dry 3) Color development-bleach-bleach-fix-rinse-stable-dry 4) Color development-bleach-bleach-fix -Stable-dry 5) Color development-fixing-bleach-fix-washing-stable-dry 6) Color development-fixing-bleach-fixing-stable-dry 7) Color development-bleach-fixing-stable-dry 8) Color development-bleach-fixing -Washing-drying 9) Color development-bleach-fixing-water washing-stable-drying 10) Black-white development-water washing-light fogging-color development-water washing-
Bleach-fixing-washing-drying 11) Black-white development-washing-light fogging-color development-bleach-fixing-stable-drying 12) Black-white development-washing-light fogging-color development-bleaching-
Bleach-fixing-Stable-dry 13) Black-white development-Washing-Reversal-Color development-Acceleration-Bleach-
Fixing-washing-stability-drying 14) Black-white development-washing-reversal-color development-bleach-fixing-stable-drying 15) Black-white development-reversal-color development-bleaching-bleach-fixing-stable-drying 16) Black-white development-washing- Reversal-color development-acceleration-bleach-fixing-stability-drying The silver halide color photographic light-sensitive material of the present invention contains various couplers.

Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, pyrazolone and closed or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD).
17643 (December 1978) Item VII-D and 18717 (December 1978 1
It is described in the patent cited in January).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use couplers in which the color former has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,401,752, No. 4,326,
No. 024, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

The magenta coupler is an oil-protected type, indazolone type or cyanoacetyl type, preferably 5
And pyrazolone-based and pyrazolazole-based couplers.

The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. , The second,
No. 600,788, No. 2,908,573, No. 3,062,653, No.
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

The pyrazolazole-based coupler is most preferably a pyrazolotriazole-based coupler, and Japanese Patent Publication No. 47-27411.
The compounds described in JP-A Nos. 59-171956 and 60-172982 are preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 1
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 59-42671, and 2,5-diacylamino-substituted phenol couplers and U.S. Patents. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

A coupler in which the color forming dye has an appropriate diffusibility can be used in combination. Such couplers are described in U.S. Pat.
Specific examples of magenta couplers are described in 237 and British Patent No. 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Application No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer except for the coupler in which the color-forming dye has diffusibility. Typical examples of polymerized dye forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,2.
It is described in No. 11. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,3.
No. 67,282.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethalhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoates (2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-aminophenol, etc.) ), Aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostear) The various couplers used in the present invention have two types in the same layer of the photosensitive layer in order to satisfy the properties required for the photosensitive material. The above may be used in combination, or the same compound may be introduced into two or more different layers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat.No. 2,322,027
No. etc. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water or ultrafiltration, and then used for coating.

Lyl lactate, trioctyl citrate, etc., aniline derivative (N, N-dibutyl-2-butoxy-5-tert)
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The silver halide emulsion used in the present invention is silver iodide, silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. The silver halide preferably transferred is silver chloride, iodobromide. Silver and silver chlorobromide.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical grains or grains close to spheres, the grain diameter is represented, and in the case of cubic grains, the edge length is represented by the grain size and the average based on the projected area), 0.1μ below 2μ
The above is preferable, but 1 μ or less and 0.15 μ or more is particularly preferable. The grain size distribution may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, octahedron, icosahedron and tetradecahedron, and may have an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsions used in the present invention are those described in Graphide, "Chemistry and Physics of Photography" [P. Glafkides. Chimie et Physique Photo
graphique (published by Paul Montel, 1967)], “Photoemulsion Chemistry” by Duffin [Photograhic Emulsion by GF Duffin
Chemistry (Focal Press, 1966)], Zecriman et al., "Manufacturing and coating of photographic emulsions" [VL Zelikman et al.
Making and Coating Potographic Emulsin (Focal Pres
s, 1964)] and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one of the simultaneous mixing methods, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method including a step of converting silver halide already formed until the completion of the silver halide grain forming step into silver halide having a smaller solubility product, An emulsion which has undergone the same halogen conversion after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, subacute salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may be present together.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 3,271,157, JP-A-51-12360).
JP-A-53-82408, JP-A-53-144319, JP-A-5
4-100717 or thioethers and thione compounds described in JP-A-54-155828 and the like, precipitation, physical aging,
It can be used in chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, the Nudel washing, the flocculation precipitation method, the ultrafiltration method and the like are used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanines); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); A noble metal sensitization method using a metal compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, Pd, Rh, and Fe in addition to a gold complex salt) can be used alone or in combination.

Of the above chemical sensitizations, sulfur sensitization alone is more preferable.

Each of the blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention is spectrally sensitized with a methine dye or the like so as to have color sensitivity. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is,
Pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nuclei, benzindolenine nuclei , Indole nucleus,
Benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thioxazolidine-2,4
A 5- or 6-membered heterocyclic nucleus such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. A typical example is U.S. Patent 2,
688,545, 2,977,229, 3,397,060, 3,522,0
52, 3,527,641, 3,617,293, 3,628,964
No., No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Patent Laid-Open No.
Nos. 52-110618 and 52-109925.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion.

The light-sensitive material produced by using the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds As a representative example. In addition, a metal complex represented by a (biskyritylamidoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
As described in U.S. Pat. No. 4,268,539, compounds having both hindered amine and hindered phenol partial structures in the same molecule give good results. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

In order to improve the storability of cyan images, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination. This UV absorber may be coemulsified with a cyan coupler.

The coating amount of the ultraviolet absorber may be an amount sufficient to impart light stability to the cyan dye image, but if used in an excessively large amount, it may cause yellowing in the unexposed portion (white background portion) of the color photographic light-sensitive material. Therefore, it is usually preferably 1 × 10 ^-4 mol / m ^2.
〜2 × 10 ^-3 mol / m ² , especially 5 × 10 ^-4 mol / m ² 〜1.5 × 10 ^-3
It is set in the range of mol / m ² .

In a conventional light-sensitive material layer structure of a color paper, an ultraviolet absorber is contained in either one of the layers adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When the ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with the color mixing inhibitor. When the ultraviolet absorber is added to the protective layer, another protective layer may be coated as the outermost layer. This protective layer may contain a matting agent having an arbitrary particle size.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based brightening agent.
Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support, as described above.
Multilayer natural color photographic materials are usually red-sensitive emulsion layers on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan.No.16, p.30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 17643 (1
December 978) and 18716 (November 1979).

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support has an oxidation property on the support. Examples include those coated with a hydrophobic resin containing a light reflecting substance such as titanium, zinc oxide, calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, Polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these embodiments.

Example-1 Table A on a paper support laminated on both sides with polyethylene.
A multi-layer color photographic paper having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (a) 19.19 and color image stabilizer (b) 4.4
To g, 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g of Ag / Kg) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ^-4 mol.
The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table I was obtained, and the coating solution for the first layer was prepared. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (7.0 × 10 ^-4 mol added per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-5 mol added per mol of silver halide) Red-sensitive emulsion layer (Addition of 1.0 × 10 ⁻⁴ mol per mol of silver halide) The following dyes were used as the dye for preventing irradiation of each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: Structural formulas of compounds such as couplers used in this example are as follows.

(A) Yellow coupler (B) Color image stabilizer (C) solvent (D) (E) Magenta coupler (F) Color image stabilizer (G) solvent 2: 1 mixture (weight ratio) (h) UV absorber (I) Color mixing inhibitor (J) Solvent (iso C ₉ H ₁₈ O ₃ P = O (k) Cyan coupler (L) Color image stabilizer (M) solvent The multi-layer color photographic paper obtained as described above was imagewise exposed and continuously processed until it was replenished with an automatic developing machine in an amount three times the volume of the color developing tank.

The stabilizing treatment was a 3-step countercurrent washing from stable to stable.
Further, the carry-in amount from the pre-bath of the bleach-fixing step and each of stable, stable and stable baths is 60 ml / m ² .

The replenishing amounts in the color developing process and the bleach-fixing process are 160 ml and 60 ml per 1 m ² of the light-sensitive material, respectively. The replenishment amount in the stabilization process is as follows.

A: Replenish 5 parts per 1 m ^{2 of} light-sensitive material with stabilizing solution.

B: Replenish 2 with 1m ^{2 of} light-sensitive material with stabilizing solution.

C: Replenish 500 parts per 1 m ^{2 of} light-sensitive material with stabilizing solution.

D: Replenish 20 ml per 1 m ^{2 of} light-sensitive material with stabilizing solution.

The liquid used in each treatment has the following formulation.

At the end of the continuous process, treat the unexposed photographic paper, dry it, and measure the yellow stain.
Aged for a day. After a lapse of time, yellow stain was measured.
The results are shown in Table-1.

As is clear from Table 1, when the replenishment amount is 5000 ml / m ² , there is no significant difference in the yellow stain with or without benzyl alcohol and the compound of the present invention, but the replenishment amount is
When the amount is reduced to 2000 ml / m ² , the stain is slightly reduced in the comparative example, sample No. 5 without benzyl alcohol (No. 6) and the compound of the present invention (0.2 g Cl) (No. 7). However, it cannot be said to be sufficient, and it can be seen that the stain can be sufficiently suppressed by including the compound of the present invention as in the present invention (No. 8) and removing benzyl alcohol. When the replenishing amount is 500 ml / m ² , the effect is more remarkable, and the method of the present invention can sufficiently suppress the stain. However, when the replenishment rate is reduced to 20 ml / m ² , although the effect of suppressing stain is somewhat obtained, it does not reach a level sufficient for practical use.

Example 2 On a subbed cellulose triacetate film support,
A sample, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver …… 0.4 Gelatin …… 1.3 Colored coupler C-1 …… 0.06 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 Second layer (intermediate layer) Fine silver bromide (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-2 …… 0.02 Dispersion oil Oil-1 …… 0.1 Third Layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, diameter / thickness ratio 2.5)
Average grain size 0.3μ) …… Silver 1.5 Gelatin …… 0.6 Sensitizing dye I …… 1.0 × 10 ^-4 Sensitizing dye II …… 3.0 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-5 Coupler C- 3 …… 0.06 Coupler C-4 …… 0.06 Coupler C-8 …… 0.04 Coupler C-2 …… 0.03 Dispersed oil Oil-1 …… 0.03 Same as above Oil-3 …… 0.012 4th layer (2nd red-sensitive emulsion layer) ) Silver iodobromide emulsion (6 mol% silver iodide, diameter / thickness ratio 3.5)
Average particle size 0.5μ) …… 1.5 Sensitizing dye I …… 1 × 10 ^-4 Sensitizing dye II …… 3 × 10 ^-4 Sensitizing dye III …… 1 × 10 ^-5 Coupler C-3 …… 0.24 Coupler C-4 ...... 0.24 Coupler C-8 ...... 0.04 Coupler C-2 ...... 0.04 Dispersed oil Oil-1 ...... 0.15 Same as above Oil-3 ...... 0.02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide Emulsion (silver iodide 10 mol%, diameter / thickness ratio 1.5
Average grain size 0.7μ) Silver 2.0 Gelatin 1.0 1.0 Sensitizing dye I 1 × 10 ^-4 Sensitizing dye II 3 × 10 ^-4 Sensitizing dye III 1 × 10 ^-5 Coupler C- 6 …… 0.05 Coupler C-7 …… 0.1 Dispersion oil Oil …… 0.01 Same as above Oil …… 0.05 6th layer (interlayer) Gelatin …… 0.1 Compound Cpd-A …… 0.03 Dispersion oil Oil-1 …… 0.05 7th Layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 6 mol%, diameter / thickness ratio 2.5)
Average particle size 0.3 μ) …… 0.7 Sensitizing dye IV …… 5 × 10 ^-4 Sensitizing dye VI …… 0.3 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Gelatin …… 1.0 Coupler C-9 ...... 0.2 Coupler C-5 ...... 0.03 Coupler C-1 ...... 0.03 Dispersion oil Oil-1 ...... 0.5 Eighth layer (second green emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, diameter) / Thickness ratio 3.5
Average particle size 0.5μ) …… 1.4 Sensitizing dye IV …… 5 × 10 ^-4 Sensitizing dye V …… 2 × 10 ^-4 Sensitizing dye VI …… 0.3 × 10 ^-4 coupler C-9 …… 0.25 coupler C-1 ...... 0.03 Coupler C-10 …… 0.015 Coupler C-5 …… 0.01 Dispersion oil Oil-1 …… 0.2 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (10 mols of silver iodide) %, Diameter / thickness ratio 1.5
Average particle size 0.7μ) Silver 1.9 Gelatin ...... 1.0 Sensitizing dye VII …… 3.5 × 10 ^-4 Sensitizing dye VIII …… 1.4 × 10 ^-4 Coupler C-11 …… 0.01 Coupler C-12 …… 0.03 Coupler C-13 0.20 Coupler C-1 0.02 Coupler C-15 0.02 Dispersion oil Oil-1 0.20 Same as above Oil-2 0.05 0.05 10th layer (yellow filter layer) Gelatin 1.2 1.2 Yellow colloid Silver …… 0.16 Compound Cpd-B …… 0.1 Dispersion oil Oil-1 …… 0.3 Eleventh layer (first blue sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, diameter / thickness ratio)
1.5 Average particle diameter 0.3μ) ...... Silver 1.0 Gelatin ...... 1.0 Sensitizing dye IX …… 2 × 10 ^-4 Coupler C-14 …… 0.9 Coupler C-5 …… 0.07 Dispersion oil Oil-1 …… 0.2 12th Layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 mol%, diameter / thickness ratio 1.5 average grain size 1.5μ) ...... Silver 0.9 gelatin ...... 0.6 Sensitizing dye IX ...... 1 × 10 ^-4 Coupler C-14 …… 0.25 Dispersion oil Oil-1 …… 0.07 13th layer (first protective layer) Gelatin …… 0.8 UV absorber UV-1 …… 0.1 Same as above UV-2 …… 0.2 Dispersion oil Oil− 1 …… 0.01 Dispersion oil Oil-2 …… 0.01 14th layer (2nd protective layer) Fine particle brominating agent (average particle size 0.07μ) …… 0.5 Gelatin …… 0.45 Polymethylmethacrylate particles (diameter 1.5μ) ・ ・ ・… 0.2
Hardener H-1 ... 0.4 Formaldehyde scavenger S-1 ... 0.5 Formaldehyde scavenger S-2 ... 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above is sample 101
And

The chemical structural formulas or names of the compounds used in this example are shown below: Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate The multi-layer color negative film thus obtained is
After cutting to a width of mm, a standard subject was photographed outdoors. This was continuously processed using the automatic developing machine with the processing steps shown in Table 2 and the following processing solutions. The processing conditions are shown in Table-2 and Table-3.

In the above treatment step, the washing with water was a countercurrent washing method from to. Next, the composition of each processing liquid will be described.

<< Washing Water, Replenishing Washing Water >> Described in Table-3 Table 3 shows the treatment steps and the details of the treatment performed.

After continuous treatment for 20 days under the above conditions, the color negative film was similarly cut into a width of 35 mm, and the color temperature was adjusted to 4800 K with a filter using a tungsten light source. After exposure to a wet exposure of 250 CMS, each of the above continuous treatments was similarly processed by passing through an automatic developing machine, and the minimum density of yellow was measured. The results are shown in Table-4.

As is clear from Table 4, especially when the amount of replenishment water is decreased, the yellow stain is remarkably increased in the absence of the compound of the present invention. However, when the compound of the present invention is contained and benzyl alcohol is removed, the stain is increased. It can be seen that it is sufficiently suppressed.

(Example-3) A color photographic light-sensitive material was prepared by applying the following first to eleventh layers to a paper support laminated on both sides with polyethylene in multiple layers. On the coating side of the first layer of polyethylene, titanium white is contained as a white pigment and a slight amount of ultramarine is contained as a bluish dye.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

1st layer (antihalation layer) Black colloidal silver ...... 0.10 Gelatin ...... 2.0 2nd layer (low sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dye (* 5 and * 4) Emulsion (3.5 mol% silver iodide, average grain size 0.7μ) ... Silver
0.15 Gelatin ...... 1.0 Cyan coupler (* 3-1) ...... 0.20 Cyan coupler (* 3-2) ...... 0.11 Anti-fading agent (* 2) ...... 0.15 Coupler solvent (* 18 and * 1) ...... 0.06 No. Three layers (high-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (* 5 and * 4) (8.0 mol% silver iodide, average grain size 0.7μ) .... Silver
0.10 Gelatin ...... 0.50 Cyan coupler (* 3-1) ...... 0.07 Cyan coupler (* 3-2) ...... 0.04 Anti-fading agent (* 2) ...... 0.05 Coupler solvent (* 18 and * 1) ...... 0.02 No. 4 layers (intermediate layer) Yellow colloidal silver …… 0.02 Gelatin …… 1.00 Color mixing inhibitor (* 14) …… 0.08 Color mixing inhibitor solvent (* 13) …… 0.16 Polymer latex (* 6) …… 0.16 Fifth layer (Low-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (* 12) (2.5 mol% silver iodide, average grain size 0.4μ) …… Silver 0.20 Gelatin …… 0.70 Magenta coupler (* 11) ...... 0.40 Anti-fading agent A (* 10) ...... 0.05 Anti-fading agent B (* 9) ...... 0.05 Anti-fading agent C (* 8) ...... 0.02 Coupler solvent (* 7) ...... 0.15 6 layers (high-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (* 12) (3.5 mol% silver iodide, average grain) 0.9 μ) ...... Silver 0.20 Gelatin ...... 0.70 Magenta coupler (* 11) ...... 0.40 Anti-fading agent A (* 10) ...... 0.05 Anti-fading agent B (* 9) ...... 0.05 Anti-fading agent C (* 8) ) …… 0.02 Coupler solvent (* 7) …… 0.15 7th layer (yellow filter layer) Yellow colloidal silver …… 0.20 Gelatin …… 1.00 Color mixing inhibitor (* 14) …… 0.06 Color mixing inhibitor solvent (* 13)… 0.24 Irradiation prevention dye (* 21, * 22) Eighth layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (* 16) (2.5 mol% silver iodide, average) Particle size 0.5μ) …… Silver 0.15 Gelatin …… 0.50 Yellow coupler (* 15) …… 0.20 Coupler solvent (* 18) …… 0.05 9th layer (high sensitivity blue sensitive layer) With blue sensitizing dye (* 16) Spectrally sensitized silver iodobromide emulsion (2.5 mol% silver iodide, average grain size 1.4μ) …… Silver 0.20 Gelatin …… 0.50 Yellow coupler (* 15) …… 0.20 Coupler solvent (* 18) …… 0.05 10th layer (UV absorbing layer) Gelatin …… 1.50 UV absorber (＊ 19) …… 1.0 UV absorber solvent (＊ 18) …… 0.30 Anti-color mixing agent (* 17) ...... 0.08 11th layer (protective layer) Fine silver chlorobromide (silver chloride 77 mol%, average particle size 0.2
μ) ...... 0.07 Gelatin ...... 1.0 Hardener (* 20) ...... 0.17 The compounds used here are as follows: * 1 Dioctyl phthalate * 2 2- (2-hydroxy-3-sec-butyl) -5
t-Butylphenyl) benzotriazole * 3-1 2- [α- (2,4-di-t-amylphenoxy) butanamide-4,6-dichloro-5-ethylphenol * 3-2 4-chloro-2- (2 -Chlorobenzamide) -5- [α- (4-t-amyl-2-chlorophenoxy) octanamide] phenol * 4 5,5'-dichloro-3,3'-di (3-sulfobutyl) -9- Ethyl thiacarbonyl cyanine Na salt * 5 Triethylammonium-3- [2- {2- [3
-(3-Sulfopropyl) naphtho (1,2-d) thiazoline-2-ylidenemethyl] -1-butenyl} -3-naphtho (1,2-d) thiazoline] probansulfonate * 6 Polyethyl acrylate * 7 Phosphoric acid Trioctyl ester * 8 2,4-di-t-hexylhydroquinone * 9 Di- (2-hydroxy-3-t-butyl-5-methylphenyl) methane * 10 3,3,3 ', 3, -tetramethyl- 5,6,5 ', 6'-Tetrapropoxy-1,1'-bisspiroindane * 12 5,5'-Diphenyl-9-ethyl-3,3'-disulfopropyloxacarbocyanine Na salt * 13 Phosphoric acid-o-cresyl ester * 14 2,4-Di-t-octylhydroquinone * 15 α -Pivaloyl-α-[(2,4-dioxo-1-
Benzyl-5-ethoxyhydantoin-3-yl) -2
-Chloro-5- (α-2,4-dioxo-t-amylphenoxy) butaneamino] acetanilide * 16 triethylammonium 3- [2- (3-benzylrhodanine-5-ylidene) -3-benzoxazolinyl] propane Sulfonate * 17 2,4-di-sec-octylhydroquinone * 18 Trinonyl phosphoric acid ester * 19 5-Chloro-2- (2-hydroxy-3-t-butyl-5-t-octyl) phenylbenztriazole * 20 1,4-bis (vinylsulfonylacetamide) ethane The silver halide color reversal photographic light-sensitive material prepared as described above was cut to a width of 8.25 cm, exposed in an imagewise manner, and 50 m per day in a roll-conveying type automatic processor in the following steps.
It was continuously treated for 0 days. After continuous processing, the above sample was subjected to stepwise exposure for sensitometry and then processed by the above-mentioned automatic processor. The steps of continuous treatment and the composition of the treatment liquid were as follows. The capacity of each processing tank of the automatic processor is
The amount of the pre-bath brought in by the photosensitive material was 30 ml per 1 m ² of the photosensitive material.

The replenishment amount in the above process indicates the replenishment amount per 1 m ² of the light-sensitive material. The stabilizing bath was replenished in the tank, the overflow of the tank was led to the tank, and the overflow of the tank was led to the tank. Reverse exposure was carried out during transfer from the first washing bath to the color developing bath.

Treatment liquid composition Bleach-fixing solution Both tank solution and replenisher solution 2-mercapto-1,3,4-triazole 1.0g Ethylenediaminetetraacetic acid / disodium / dihydrate 5.0g Ethylenediaminetetraacetic acid / Fe (III) / ammonium-
Hydrous salt 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g / solution) 160.0ml Glacial acetic acid 5.0ml Add water 1 pH6.50 Stabilizer Both tank solution and replenisher ethylenediamine-N, N, N'-N'- Tetramethylenephosphonic acid 0.3 g Benzotriazole 1.0 g Water was added, and after continuous treatment with sodium hydroxide at pH 7.5, the minimum density of yellow was measured with respect to the sample subjected to stepwise exposure for sensitometry. Further, the same sample was aged at 80 ° C. for 30 days, and after the aging, the minimum density of yellow was similarly measured. The results are shown in Table-5.

From Table-5, it can be seen that Sample Nos. 1 to 4 are obtained by sequentially reducing the replenishment amount, but the stain increases as the replenishment amount decreases. On the other hand, it can be seen that the presence of benzyl alcohol increases the stain when the replenishment ratio is 50 times or less, regardless of the presence or absence of the compound of the present invention (Sample No.
5, 6, 8, 10). On the other hand, when benzyl does not exist and the compound of the present invention is contained in the color developing solution,
The stain is improved (Sample Nos. 7 and 9). If the replenishment rate is reduced to 0.4, the above effect is no longer sufficient.

Claims (1)

[Claims] 1. A processing method in which a silver halide color light-sensitive material is subjected to color development processing, followed by desilvering processing, water washing processing, or stabilization processing, wherein the color development processing solution contains substantially benzyl alcohol. , And at least one compound represented by the following general formula [I] is contained, and the water washing treatment step or the stabilization treatment step is composed of a large number of tanks, and is replenished by a multi-stage countercurrent method A method for processing a silver halide color photographic light-sensitive material, characterized in that the amount is 0.5 to 50 times the amount carried in from the previous bath per unit area of the silver halide color photographic light-sensitive material to be processed. General formula [I] (M may be the same or different and represents a monovalent cation such as a hydrogen atom, an alkali metal ion or an ammonium ion.)