JPH06100805B2 - Processing method of silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color photographic developer composition and a method for processing a silver halide color photographic light-sensitive material using the same, and particularly to stability of the color developer. And the color development is improved,
In addition, the present invention relates to a color photographic developer composition in which the increase in fog during continuous processing is significantly reduced, and a processing method using the same.

(Prior Art) A color photographic developer containing an aromatic primary amine color developing agent (hereinafter simply referred to as a color developer) has been used for a long time for forming a color image, and nowadays a color photographic image is obtained. It plays a central role in the formation method. However, the above color developer has a problem that it is very easily oxidized by the presence of air or metal, and when a color image is formed by using the oxidized developer, fog is increased, sensitivity and gradation are deteriorated. It is well known that desired photographic characteristics cannot be obtained due to changes.

Therefore, various means for improving the preservability of color developing solutions have been studied, and the method of using hydroxylamine and sulfite ion in combination is the most general method. However, when hydroxylamine is decomposed, ammonia is generated to cause fog, and sulfite ion has a drawback that it acts as a competing compound of a developing agent and inhibits color development. It is hard to call it a drug.

In particular, sulfite ion has long been used as a preservative for various developing agents or as an inhibitor for the decomposition of hydroxylamine, but it greatly inhibits color development, and especially when used in a system where benzyl alcohol is not present, the color density decreases significantly. To do.

Alkanoamines described in JP-A-54-3532 and polyethyleneimines described in JP-A-56-94349 have been proposed as compounds replacing sulfite, but even if this compound is used, a sufficient effect can be obtained. I couldn't get it.

In addition, various preservatives and chelating agents have been studied in order to improve the stability of color developers. For example, as preservatives, there are JP-A Nos. 52-49828 and 59-16014.
2, No. 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat.No. 3,746,544, U.S. Pat.
Hydroxylcarbonyl compounds described in No. 3 and British Patent No. 1,306,176, α-aminocarbonyl compounds described in JP-A Nos. 52-143020 and 53-89425, alkanolamines described in JP-A-54-3532, and JP-A No. 54-3532. 57-44148 and 57-537
Examples thereof include metal salts described in JP-A No. 49, and hydroxamic acid described in JP-A No. 52-27638. As the chelating agent, aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44-30232, JP-A-56-97347, JP-B-56-3
Organic phosphonic acids described in 9359 and West German Patent 2,227,639, JP-A-52-102726, JP-A-53-42730, and JP-A-54-121127.
Nos. 55-126241 and 55-65956, and other phosphonocarboxylic acids, and JP-A-58-195845 and 58-2034.
Examples thereof include compounds described in JP-B No. 40 and JP-B-53-40900.

(Problems to be Solved by the Invention) However, even if these conventional techniques are used, satisfactory results cannot be obtained due to insufficient preserving performance, adverse effects on photographic characteristics, and merits and demerits. .

Further, the color photographic light-sensitive material containing a silver chlorobromide emulsion having a high chlorine content is apt to cause fog during color development as described in JP-A-58-95345 and 59-232342. When such an emulsion is used, a preservative having a low emulsion solubility and a superior preservative performance is indispensable. In this sense, development of a new developing solution is desired.

Therefore, the present invention is excellent in stability and color development, and
It is an object of the present invention to provide a processing method in which the increase in fog during continuous processing is significantly reduced.

A further object of the present invention is to provide a color developer composition having excellent stability without lowering the color density even when it does not substantially contain benzyl alcohol.

Furthermore, the present invention improves the stability of the color developer,
An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which the change with time during continuous processing or the like is remarkably reduced and the increase of fog is prevented.

(Means for Solving Problems) The above-mentioned object of the present invention is achieved by the following general formula (C-I) or (C
-II), a silver halide color photographic light-sensitive material containing a cyan coupler selected from compounds represented by the formula (II), containing substantially no benzyl alcohol, an aromatic primary amine color developing agent and the following general formula ( It was achieved by a method for processing a silver halide color photographic light-sensitive material characterized by processing with a developer containing a compound represented by I).

General formula (I) R ¹ and R ² are a hydrogen atom, an alkyl group or an aryl group, and the alkyl group or the aryl group may have a substituent. R ¹ and R ² may be the same or different, and these groups may be linked together. Substituents that the alkyl group and aryl group may have include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group, an aryloxy group, an amino group, a carboxyl group, a sulfo group, a phosphonic acid group, and carbamoyl. Group, sulfamoyl group, sulfonyl group, ureido group, acyl group, acylamino group, sulfonamide group, alkylthio group, arylthio group, nitro group, cyano group, etc., and these are two or more and two or more in the alkyl group and aryl group. It may be replaced. The hydroxyl group, carboxyl group and sulfo group may be salts of alkali metals (eg sodium, potassium etc.).

Preferred as R ¹ and R ² in the general formula (I) are a halogen atom, a hydroxyl group, an alkoxyl group,
An alkyl group substituted with an amino group, a carboxyl group, a sulfo group, a phosphonic acid group and a nitro group and an unsubstituted alkyl group.

The total carbon number in the general formula (I) is preferably 30 or less, more preferably 20 or less.

The addition amount of the compound represented by the general formula (I) according to the present invention is 0.1 g to 30 g, preferably 0.5 g to 10 g per 1 color developing solution.

In the present invention, the developer composition is meant to include, in addition to the color developer itself, a concentrated solution of the color developer containing at least an aromatic primary amine color developing agent and the compound of the general formula (I). is there.

Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

The compound represented by the general formula (I) can be easily obtained as a commercial product. Further, it can be easily synthesized by applying the method of Organic Synthesis (Organic Synthesis) II, 204 or Organic Synthesis (Organic Synthesis) IV, 299.

The color developer of the present invention will be described below.

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 representative 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 4-amino-3-methyl -N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine 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 have a counter ion and may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 per developing solution.
The concentration is from 1 g to about 20 g, more preferably from about 0.5 g to about 10 g.

In particular, when the color developing agent D-6 is used in the presence of the compound of the general formula (I), it is preferable in that the increase of fog is small and good photographic characteristics can be obtained.

The compound of the general formula (I) has particularly remarkable preservative performance, especially in a system using an aromatic primary amine color developing agent, in combination with a compound which directly stabilizes the main agent. Here, compounds that directly stabilize are generally known as antioxidants (preservatives), and examples thereof include compounds described below such as hydroxylamines.

As the hydroxylamines used in the color developing solution used in the present invention, the compound represented by the general formula (II) is particularly preferable.

General formula (II) In the formula, R ³ and R ⁴ represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R ³ and R ⁴ are alkyl groups or alkenyl groups, and it is more preferable that at least one of them has a substituent. R ³ and R ⁴ may be linked to form a heterocycle together with the nitrogen atom.

The alkyl group and alkenyl group may be linear, branched, or cyclic, and the substituent is a halogen atom (F, Cl, Br
Etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy groups (phenoxy group, etc.), sulfonyl groups (methanesulfonyl group, p-
Toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group,
Unsubstituted sulfamoyl group), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (fuhtamido group, benzamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group ( Methoxycarbonylamino group), allyloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, Sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.), arylthio group (phenylthio group, etc.), and heterocyclic group (morpholyl group, pyridyl group, etc.) ) Can be mentioned. Where R ³ and R ⁴ may be the same or different, and
The substituents on R ³ and R ⁴ may be the same or different.

The carbon number of R ³ and R ⁴ is preferably 1-10, and particularly preferably 1-5. Examples of the nitrogen-containing heterocycle formed by connecting R ³ and R ⁴ include piperidyl group, pyrrolidylyl group, N-alkylpiperazyl group, morpholyl group, indolinyl group, benztriazolyl group and the like.

Preferred substituents for R ³ and R ⁴ are hydroxy, alkoxy, alkyl or aryl sulfonyl, amide, carboxy, cyano, sulfo, nitro and amino groups.

Specific examples of the compound represented by formula (II) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

II- (34) NH ₂ OH The compound represented by the general formula (II) can be synthesized by the known method shown below.

U.S. Pat.Nos. 3,661,996, 3,362,961 and 3,293,034
No. 3, Japanese Examined Patent Publication No. 42-2794, U.S. Patent Nos. 3,491, 151 and 3,
655,764, 3,467,711, 3,455,916, 3,2
Nos. 87,125 and 3,287,124 These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

The amount of the compound represented by the general formula (II) added to the color developing solution is preferably 0.1 g to 20 g per color developing solution,
It is more preferably 0.5 g to 10 g.

In addition, as compounds other than hydroxylamines,
Hydrazines, hydrazides, sugars and hydroxamic acids are particularly preferable.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be added if necessary. The addition amount of these is 0 g to 20 g / l, preferably 0 g to 5 g / l,
If the stability of the color developing solution is maintained, it is preferably as small as possible.

As other preservatives, hydroxyacetones described in U.S. Pat. No. 3,615,503 and British Patent 1,306,176, JP-A-52-
Α-aminocarbonyl compounds described in 143020 and 53-89425, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727, 59-
Α, α'-dicarbonyl compounds described in 160141, 59-1
If necessary, salicylic acids described in No. 80588, gluconic acid derivatives described in No. 56-75647, etc. may be contained, and two or more kinds of these preservatives may be used in combination as necessary.

It is particularly preferable to add an aromatic polyhydroxy compound.

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, trishydrocyaminomethane 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, since they have the advantages of being free from adverse effects (fogging, etc.) and being 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 developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents 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.

The chelating agent is preferably an organic acid compound, for example, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359, and West German Patent 2,227,639. Organic phosphonic acids, JP-A-52-
102726, 53-42730, 54-121127, 55-126241
No. and 55-65956 and the like phosphonocarboxylic acids,
Others JP-A-58-195845, JP-A-58-203440 and JP-B-53
-40900 etc. can be mentioned. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid Diethylenetriamine pentaacetic acid Ethylenediaminetetraacetic acid Triethylenetetramine hexaacetic acid N, N, N-trimethylenephosphonic acid Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1,3-diamino-2-propanol- Tetraacetic acid transcyclohexanediaminetetraacetic acid nitrilotriapropionic acid 1,2-diaminopropanetetraacetic acid hydroxyethyliminodiacetic acid glycol ether diaminetetraacetic acid hydroxyethylenediamine triacetic 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 These chelating agents may be used in combination of two or more, if necessary.

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.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and fog prevention. Here, "substantially" means that the amount per color developing solution is not more than 2 ml, preferably not 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 Japanese Patent Publication No. 52-498
29 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30074
Quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, US Pat.
P-Aminophenyls described in 4,119,462, US Patent
2,494,903, 3,128,182, 4,230,796, 3,25
3,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546,
2,596,926 and 3,582,346 and the like amine compounds, JP-B-37-16088, 42-25201, U.S. Pat.
No. 183, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. patents
If necessary, polyalkylene oxides represented by 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

In the present invention, any antifoggant can be added if necessary. Antifoggants include sodium chloride,
Alkali metal halides such as potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole,
Nitrogen-containing heterocyclic compounds such as 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-bezotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazoles, hydroxyazaindolizine and adenine Can be given as a representative example.

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

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, 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 replenishment amount is preferably small, but 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.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the processing method of the present invention will be described.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular, an organic complex salt of iron (III) (for example, aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid). Acids, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, malic acid; persulfates;
Hydrogen peroxide and the like are preferred. Of these, iron (III)
The organic complex salt of is particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β -Oxyethyl) -N, N ',
N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetramine hexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propanoltetraacetic acid , Methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diaminotetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine dipropionacetic acid, phenylenediamine tetraacetic acid, 2-phosphonobutane-1, 2,4-triacetic acid, 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3 -Propylenediamine-N, N, N ',
Examples thereof include N'-tetramethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution by using a ferric salt and a chelating agent, one or more ferric salts may be used. 1 more chelating agent
You may use 2 or more types. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.0 m.
ol / l, preferably 0.05 to 0.50 mol / l.

A bleaching accelerator can be used in the bleaching agent or the bleach-fixing agent, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent No. 1,2.
90,812, 2,059,988, JP-A-53-32736, 53-
57831, 53-37418, 53-65732, 53-72623
No. 53, No. 53-95630, No. 53-95631, No. 53-104232, No. 5
3-124424, 53-141623, 53-28426, Research Disclosure No. 17129 (July 1978) and other compounds having a mercapto group or a disulfide group; JP-A-50-140129 Thiazolidine derivatives as described in JP-B-45-8506, JP-A-52-20832 and JP-A-5-20832.
3-32735, 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 described in West German Patents 966,410 and 2,748,430. Oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434,
49-59644, 53-94927, 54-35727, 55-26506
And the compounds described in JP-A No. 58-163940, iodine, bromide ion and the like. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferable.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (eg potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg iodide). Ammonium) rehalogenating agents can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Add one or more types of inorganic acids having pH buffering ability such as sodium phosphate, citric acid, sodium citrate, tartaric acid, organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. You can

The bleach-fixing solution or the fixing agent used in the fixing solution in the present invention is a known fixing agent, that is, sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; Thiocyanates such as sodium thiocyanate and ammonium thiocyanate; Water-soluble salts such as ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1.8-octanediol and thioureas It is a silver halide dissolving agent, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol,
More preferably, it is in the range of 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is 3
-10 are preferable, and 5-9 are especially preferable. 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 contrary, 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.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

In the present invention, the bleach-fixing solution and fixing solution include sulfites (such as sodium sulfite, potassium sulfite and ammonium sulfite) as preservatives, bisulfites (such as ammonium bisulfite, sodium bisulfite and potassium bisulfite) and meta. It contains a sulfite ion-releasing compound such as bisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are about 0.02-0.50 mol in terms of sulfite ion.
/ l is preferably contained, more preferably 0.04 ~
It is 0.40 mol / l.

As the preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added as required.

Next, the water washing step of the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" without providing a substantial water washing step in place of the usual "water washing treatment" can be used. As described above, the “water washing treatment” in the present invention is used in a broad sense as described above.

The rinsing water amount of the present invention is difficult to define because it varies depending on the number of multi-stage countercurrent rinsing baths and the amount of the pre-bath component of the light-sensitive material introduced, but in the present invention, the bleaching and fixing solution components in the final rinsing bath are Is 1 × 10 ⁻⁴ or less. Eg 3
In the case of countercurrent washing with water in a tank, it is preferable to use about 1000 ml or more, and more preferably 5000 ml or more per 1 m ² of the light-sensitive material. Also, in the case of water-saving treatment, 100 to ¹⁰ per 1 m ² of light-sensitive material
It is recommended to use 00 ml.

The washing temperature is 15 ° C to 45 ° C, more preferably 20 ° C to 35 ° C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial・ Anti-Fungal Agents "(J.Antibact.Antifung.Agents) Vol.11, No.5, p2
07 to 223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal Agents", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or drying load and unevenness. If necessary, a surfactant or the like for preventing the above can be added. Or by West, "Photographic Science
And Engineering Magazine (Phot.Sci.Eng.), 6th
Vol., Pp. 344-359 (1965), etc. may be added. In addition, using ion-exchanged water as described in Japanese Patent Application No. 61-131632 is also an effective means for improving the stability of washing water.

Furthermore, the present invention is particularly effective in the case of adding a chelating agent, a bactericidal agent, and an antifungal agent to the washing water to significantly reduce the amount of washing water by a multistage countercurrent water flow of two or more tanks. Also,
It is also particularly effective when a multistage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the ordinary water washing step. In these cases, the bleaching and fixing components in the final bath are 5 × 10 ^-2 or less, preferably 1 ×
It should be 10 ^-2 or less. Further, a method of significantly reducing the amount of water by using only distilled water or water such as ion-exchanged water from which calcium ions and magnesium ions in the water are significantly removed is also effective.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg pH 3 ~
8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. Are used in combination) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole, etc.) ), Various additives such as surfactants, optical brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate for adjusting the film pH of the processor in order to improve the image storability.

In the case where the amount of washing water as described above is significantly reduced, it is preferable for the purpose of reducing the amount of drainage to allow a part or all of the overflow water of washing water to flow into the bleach-fixing bath or the fixing bath which is the pre-bath.

In this treatment step, a constant finish can be obtained by using a replenisher of each treatment solution to prevent the composition of the solution from changing during continuous processing. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

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 method of the present invention is a process using a color developing solution,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color positive film, color negative film, color reversal film and the like, but it is particularly preferably applied to color paper and color reversal paper.

The silver halide emulsion of the light-sensitive material to which the processing method of the present invention is applied can be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, and silver chloride, but rapid processing and low replenishment processing are possible. In the case of carrying out, the silver chlorobromide emulsion or silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the case where the content of silver chloride is 80 to 100 mol% is particularly preferable.
In addition, high sensitivity is required, and during manufacturing, storage, and / or
Alternatively, when it is necessary to suppress fog during processing to a particularly low level, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide is preferable, and 70 mol% or more is more preferable. When the silver bromide content is 90 mol% or more, rapid processing becomes difficult, but means for promoting development, such as means for causing a development accelerator such as a silver halide solvent, a fogging agent, or a developer described below to act during processing. By using, it is possible to accelerate the development to some extent without being limited by the content of silver bromide,
It may be preferable. In any case, it is not preferable to contain a large amount of silver iodide, and the amount may be 3 mol% or less.

In the present invention, the silver halide grains of the silver halide emulsion may have different phases in the inside and surface layers, 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 average grain size based on the projected area. Tabular grains In the case of, it is also expressed in terms of sphere.) Is preferably 2μ or less and 0.1μ or more,
Particularly preferred is 1.5 μ or less and 0.15 μ or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size 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). Those having a variation rate are preferable) can 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 have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may have different crystal forms or coexist with them, may have an irregular (irreguler) crystal form such as spherical shape, 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 as a seed on the surface or an internal latent image type which forms inside a grain.

The photographic emulsion used in the present invention is described by Graphide in "Chemistry and Physics of Photography" [P. Glafkides, Chimieet Physique Photog.
raphique (Paul Motel, 1967)], Duffin's "Photoemulsion Chemistry" [GF Duffin Photograhic Emulsion
Chemistry (Focal Press, 1966)], Zelikmann et al., "Manufacturing and coating of photographic emulsions" [VL Zelikmen et al "M
aking and Coating Photographic Emulsion (Focal Pre
ss, 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. Simultaneous mixing method 1
As one form, a method of keeping pAg constant in a 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 by the time the silver halide grain forming step is completed into a silver halide having a smaller solubility product, and a halide Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, copper salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt,
An iron salt or an iron complex salt may coexist.

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

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-54-
The thioethers and thione compounds described in 100717 or JP-A-54-155828 can be used for precipitation, physical aging and chemical aging. To remove the soluble silver salt from the emulsion after physical ripening, noodle washing, flocculation sedimentation method, ultrafiltration method or the like is 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, rhodanins); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); metals A noble metal sensitization method using a compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, Pd, Rh, Fe, etc. in addition to a gold complex salt) can be used alone or in combination.

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, a pyrroline nucleus, an oxazoline ring, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a 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-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and 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 US Patent No.
No. 2,688,545, No. 2,977,229, No. 3,397,060, No. 3,522,052, No. 3,527,641, No. 3,617,293,
No. 3,628,964, No. 3,666,480, No. 3,672,898
No. 3, No. 3,679,428, No. 3,703,377, No. 3,769,30
No. 1, No. 3,814,609, No. 3,837,862, No. 4,026,7
07, British Patents 1,344,281, 1,507,803, Japanese Patent Publication
43-4936, 53-12375, JP-A-52-110618, 52-1
It is described in 09925.

A dye that does not itself have a spectral sensitizing effect 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.

These sensitizing dyes may be added during grain formation, before or after chemical sensitization, during chemical sensitization, or during coating. Addition at the time of grain formation is effective not only for enhancing adsorption but also for controlling the crystal shape and the grain internal structure. Further, addition during chemical sensitization is effective not only for enhancing adsorption but also for controlling chemical sensitization sites and preventing crystal deformation. In the case of an emulsion containing a high content of silver chloride, these addition methods are particularly effective, and it is also particularly useful to apply them to grains having an increased content of silver bromide or silver iodide on the grain surface. is there.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

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 described in JP-B-58-10739, U.S. Patent No. 4,401,752, No. 4,326,0
No. 24, 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 coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. 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. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
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.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in US Pat. No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230
(June 1984), and pyrazolopyrazoles. The imidazo [1,2−] described in European Patent No. 119,741 in view of the small yellow sub-absorption of the coloring dye and the light fastness.
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

In the method of the present invention, the general formula (C-I) or (C-II)
Cyan couplers that can be used in combination with the cyan coupler represented by are various oil-proteclo-type naphthol-based and phenol-based couplers, and U.S. Pat. No. 2,474,293
The naphthol couplers described in U.S. Pat. No. 4,052,212, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200, which are oxygen atom-releasing two-equivalent naphthol couplers are typical examples. .
Further, specific examples of the phenol-based coupler are described in US Pat.
No. 9,929, No. 2,801,171, No. 2,772,162, No. 2,8
No. 95,826. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention,
Typical examples thereof include phenol cyan couplers having an alkyl group of ethyl group or more at the meta 1-position of the phenol nucleus described in U.S. Pat. No. 3,772,002, U.S. Pat.
No. 2,772,162, No. 3,758,308, No. 4,126,396, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,32
2,5-described in 9,729 and JP-A-58-42671
Diacylamino-substituted phenol couplers and U.S. Pat.Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767, and the like, which has a phenylureido group at the 2-position and has an acylamino group at the 5-position. Examples include phenolic couplers having a group.

In the processing method of the present invention, it should be noted that the use of at least one cyan coupler represented by the following general formulas (C-I) and (C-II) resulted in less fog and good photographic properties. That is.

The general formulas (C-I) and (C-II) are described in detail below.

General formula (C-I) (In the formula, R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ⁶ represents an alkyl group or an aryl group. R ⁷ represents a hydrogen atom, a halogen atom,
An alkyl group or an alkoxy group is shown. R ⁷ may combine with R ⁶ to form a ring. Z ¹ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ⁸ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ⁹ represents an alkyl group having 2 or more carbon atoms. R ¹⁰ represents a hydrogen atom, a halogen atom or an alkyl group. Z ² represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.) Of the general formula (CI) and the general formula (C-II) in the cyan coupler of R ^5, R ⁶ and R ^8, for example, the alkyl group of 1 to 32 carbon atoms, a methyl group, butyl group, tridecyl group, a cyclohexyl group, an allyl group, and examples of the aryl group for example, Examples thereof include a phenyl group and a naphthyl group, and examples of the heterocyclic group include 2-pyridyl group and
A 2-imidazolyl group, a 2-furyl group, a 6-quinolyl group and the like can be mentioned. These groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group, a 2-methoxyethoxy group, etc.), an aryloxy group (for example, a 2,4-di-tert-amylphenoxy group, 2-
Chlorophenoxy group, 4-cyanophenoxy group, etc.),
Alkenyloxy group (for example, 2-propenyloxy group), acyl group (for example, acetyl group, benzoyl group, etc.), ester group (for example, butoxycarbonyl group,
Phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (eg, acetylamino group,
Methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group), imide group, (eg, succinimide group, Hydantoinyl group), ureido group (eg, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, Ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, sulfo group, halogen atom and the like.

Further, the amino group of R ⁵ may be substituted or unsubstituted. Examples of the substituent in the case of substituting here include those mentioned above. Examples of the substituted amino group for R ⁵ include an anilino group and a benzothiazolylamino group.

In the general formula (CI), when R ⁷ is a substitutable substituent, it may be substituted with the optionally substituted substituent described for R ⁵ .

Examples of the optionally substituted alkyl group having at least two carbon atoms represented by R ^{9 in} the general formula (C-II) include an ethyl group, a propyl group, a butyl group, a pentadecyl group, and a tert-
Examples thereof include a butyl group, a cyclohexyl group, a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group.

In formulas (C-I) and (C-II), Z ¹ and Z ² each represent a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter). , A halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, etc.) alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (eg, 4-chlorophenoxy group, 4 -Methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy group etc.), sulfonyloxy group (eg methanesulfonyloxy group, toluenesulfonyloxy group etc.) , An amide group (for example, a dichloroacetylamino group, a heptafluorobutyrylamino group, a methanesulfonylamino group, a toluenesulfonylamino group, etc.), an alkoxycarbonyloxy group (for example, an ethoxycarbonyloxy group, Group), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (eg, , Succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.) and the like. These leaving groups may include groups useful for photography.

Preferred examples of the cyan coupler represented by the general formula (C-I) or (C-II) are as follows.

In formula (C-I), preferred R ⁵ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
A carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group are more preferable.

In the general formula (CI), when R ⁷ and R ⁶ do not form a ring, R ⁶ is preferably a substituted or unsubstituted alkyl group,
An aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ⁷ is preferably a hydrogen atom.

In formula (C-II), R ⁸ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In formula (C-II), preferred R ⁹ is a methyl group having an alkyl group having 2 to 15 carbon atoms and a substituent having 1 or more carbon atoms, and the substituent includes an arylthio group, an alkylthio group, an acylamino group and an aryloxy group. Groups and alkyloxy groups are preferred.

In formula (C-II), R ⁹ is more preferably an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

In formula (C-II), preferred R ¹⁰ is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

Preferred in the general formulas (C-I) and (C-II)
Z ¹ and Z ² are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group, respectively.

In formula (C-II), Z ² is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In formula (CI), Z ¹ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

Specific examples of the cyan couplers represented by the general formulas (C-I) and (C-II) are shown below, but the present invention is not limited thereto.

The cyan couplers represented by the above general formulas (C-I) and (C-II) are disclosed in JP-A-59-166956 and JP-B-49-11572.
It can be synthesized based on the description such as No.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Pat.No. 4,366,237 and British Patent 2,12.
Specific examples of magenta couplers are described in 5,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a duplex or more. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material. The above can be introduced.

The coupler used in the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 17
After being dissolved in either a single solution of a high boiling organic solvent having a boiling point of 5 ° C or higher and a so-called auxiliary solvent having a low boiling point, or a mixed solution of both, finely dispersed in an aqueous medium such as water or a gelatin aqueous solution in the presence of a surfactant. . Examples of high boiling organic solvents are described in US Pat. No. 2,322,027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, or ultrafiltration, and then used for coating.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyldildiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trichloropropylphosphate, di2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.) ), Aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citre) Etc.), aniline derivatives (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 or higher,
Preferably, an organic solvent having a temperature of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, 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.

Standard usage of color couplers is in the range of 0.001 to 1 mole per mole of light-sensitive silver halide, preferably 0.01 to 0.5 moles for yellow couplers, 0.003 to 0.3 moles for magenta couplers, and for cyan couplers. 0.002 is 0.3 mol.

The light-sensitive material to which the method of the present invention can be applied is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, or a sulfonamidephenol derivative as a color antifoggant or color mixing inhibitor. Etc. may be contained.

A known anti-fading agent can be used in the light-sensitive material to which the method of the present invention is applied. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Typical examples thereof include ethers or ester derivatives in which the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines and these compounds are silylated or alkylated. Further, a metal complex represented by (bissalicylaldoximate) nickel complex and (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol substructures in the same molecule, as described in US Pat. No. 4,268,593, 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.
To 2 × 10 ⁻³ mol / m ² , especially 5 × 10 ⁻⁴ mol / m ^{2 to} 1.5 × 10
It is set in the range of ^-3 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 tank, another protective layer may be coated as the outermost layer. The protective layer may contain a matting agent having an arbitrary particle size.

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

The light-sensitive material to which the present invention is applied, as a filter dye,
Alternatively, a water-soluble dye may be contained in the hydrophilic colloid layer for various purposes such as prevention of irradiation or halation. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green light and red light are particularly preferable.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material to which the present invention is applied 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,
At least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer
Have one. 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 to which the present invention is applied is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer and a back layer in addition to the silver halide emulsion layer.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material to which the present invention is applied, 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 and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly A variety of synthetic hydrophilic polymeric substances such as acrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers can be used. The use of acrylic acid-modified polyvinyl alcohol in the protective layer is particularly useful, and even more useful for rapid processing with high silver chloride content emulsions.

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

The light-sensitive material to which the present invention is applied, in addition to the above-mentioned additives,
Further, it is useful in various stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof as described above, lubricants, mordants, matting agents, antistatic agents, plasticizers and other photographic light-sensitive materials. Various additives may be added. Typical examples of these additives are Research Disclosure 17643 (December 1978) and 18716 (November 1979).
Month).

"Reflective support" that can be used in the light-sensitive material to which the present invention is applied
Is for enhancing the reflectivity to make the dye image formed on the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, calcium carbonate, calcium sulfate on the support. And those coated with a hydrophobic resin containing a light reflecting substance 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, polyester film of cellulose triacetate or cellulose nitrate, polyamide film , Polycarbonate film, polystyrene film, etc.,
These supports can be appropriately selected depending on the purpose of use.

(Effect of the Invention) The developer composition of the silver halide color photographic light-sensitive material of the present invention is excellent in preservability and color development, and provides a color developer in which the increase of fog during continuous processing is remarkably reduced.

The effects described above are further enhanced by using the developer composition of the present invention in a system containing substantially no benzyl alcohol.

By using the developer composition of the present invention, stability can be increased and deterioration of color development can be prevented without using a substance such as sulfite ion which acts as a competing compound of a developing agent.

Further, according to the method for processing a silver halide color photographic light-sensitive material using the developer composition of the present invention, the generation of stains during continuous processing can be significantly reduced.

(Example) The present invention will be described in more detail based on an example.

Reference Example As color developing solutions, processing solution samples Nos. 1 to 20 having the following formulations were prepared.

Color developer Compound (A) shown in Table 1 below Amount shown in Table 1 below Compound (B) shown in Table 1 below Amount shown in Table 1 below Sodium sulfite 0.2g Potassium carbonate 30g Ethylenediaminetetraacetic acid ( EDTA) ・ Disodium 1g Sodium chloride 1.5g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline ・ sulfate 5.0g Whitening agent (4,4'- Diaminostilbene type) 3.0 g Water is added to 1000 ml pH 10.05 Sample No. 1 to 20 of the color developer prepared in this way are put in a test tube so that the opening ratio (opening area / sample volume) is 0.06 cm ^-1. And placed at 35 ° C. for 4 weeks. After 4 weeks, the decrease due to evaporation was corrected with distilled water, and the residual ratio of the aromatic primary amine color developing agent was measured by liquid chromatography and calculated. The results are shown in Table 1.

As is clear from Table 1, by adding compounds such as triethanolamine or polyethyleneimine or sodium sulfite to hydroxylamine and diethylhydroxyamine alone (Sample Nos. 1 and 2), the above developing agent is added. The residual rate of is improved but is not sufficient (Sample Nos. 3, 4, 5).

However, as is apparent from Sample Nos. 6 to 20, by using the compound represented by the general formula (I), the residual ratio of the developing agent is remarkably improved and the preservability of the color developing solution is improved. I understand that Above all, sample Nos. 11 and 12
As is apparent from the above, the combined use of the compound represented by the general formula (I) and the exemplified compound (II) -5 markedly improves the homeostasis.

Example 1 A multilayer color photographic paper material was prepared by coating each layer having the composition shown in Table B below on a paper support laminated on both sides with polyethylene. The coating liquid for each layer was prepared as follows.
The structural formulas and the like of the couplers, color increase stabilizers, etc. used in the coating liquid will be described later.

Preparation of coating solution for the first layer Yellow coupler (a) 19.1 g 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 / kg of Ag) 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 B was obtained, and the coating solution for the first layer was prepared.
Each of the components shown in Table B is used to form the coating liquid for the second to seventh layers as well.
It was prepared in the same manner as the layer coating solution. As the 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 the emulsion of each layer.

(B) Spectral sensitizer for blue-sensitive emulsion (7 × 10 ^-4 mol added per mol of silver halide) (b) Spectral sensitizer for green-sensitive emulsion (4 × 10 ^-4 mol added per mol of silver halide) (C) Spectral sensitizer for red-sensitive emulsion (2 × 10 ⁻⁴ mol added per mol of silver halide) The following dye was used as an anti-irradiation dye for each emulsion layer.

Dye for green sensitive emulsion layer Dye for red-sensitive emulsion layer The structural formulas of the compounds used in this example, such as couplers, are as follows.

(A) Yellow coupler (B) Color image stabilizer (C) solvent (D) Color mixing inhibitor (E) Magenta coupler (F) Color image stabilizer (G) solvent (H) UV absorber (I) Color mixing inhibitor (J) Solvent (iso C ₉ H ₁₈ 0 _{3 3} P = 0 (k) Cyan coupler (1) Color image stabilizer (M) solvent Various multilayer color photographic papers prepared as described above were wedge-shaped exposed and then processed in the following processing steps.

(Processing process) (Temperature) (Time) Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Stable 1 35 ℃ 20 seconds Stable 2 35 ℃ 20 seconds Stable 3 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Stabilizer It was a 3 tank countercurrent wash from 3 to 1. The formulation of each treatment liquid used is as follows.

Color developer Additive shown in Table 2 below (C) Amount shown in Table 2 Additive shown in Table 2 below (D) Amount shown in Table 2 Benzyl alcohol Amount shown in Table 2 Diethylene glycol No. Amount shown in Table 2 Sodium sulfite 0.2g Potassium carbonate 30g Nitrilotriacetic acid 1g Sodium chloride 1.5g Color developing agent shown in Table 2 below 0.01mol Whitening agent (4,4'-diaminostilbene type) 3.0g Potassium bromide added 0.01g water 1000 ml pH 10.05 bleach-fixing solution _{EDTAFe (III) NH 4 · 2H} 2 O 60g EDTA · 2Na · 2H 2 O 4g ammonium thiosulfate (70%) 1000 ml by addition of 120ml sodium sulfite 16g glacial acetic 7g water pH 5.5 Stabilizer Formalin (37%) 0.1ml 1-Hydroxyethylidene-1,1'-diphosphonic acid (60%) 1.6ml Bismuth chloride 0.35g Ammonia water (26%) 2.5ml Nitrilotriacetic acid ・ 3Na 1.0g EDTA 0.5g Sodium sulfite 1.0g 5 Chloro-2-methyl-4-isothiazolin-3-one 50 mg Water was added to 1000 ml On the other hand, a part of the above color developing solution was placed in a beaker 1 and allowed to stand at 35 ° C for 21 days in an open system. Used in the above treatment process.

The treatment using the color developer (aging liquid) left for 21 days is tested with the aging liquid, and the color developing liquid before being left (fresh liquid)
Was treated as a fresh liquid test.

The photographic properties obtained by the fresh liquid test and the aged liquid test are
Shown in the table.

The photographic properties are indicated by two points, that is, Dmin at magenta density and gradation.

Dmin represents the minimum density, and gradation represents the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 at log E.

From the results shown in Table 2, in Experiment Nos. 1 to 4, Dmin and gradation change with time, and the contrast becomes high, while in Experiment Nos. 5 to 5.
It can be seen that in No. 18, changes in Dmin and gradation are small even after aging, and the stability of photographic properties is remarkably improved. Also experiment
Experiment No. 8 has the smallest changes in Dmin and gradation among Nos. 5 to 8, and it is understood that Compound D is the most preferable among the color developing agents. Further, comparison of Experiment Nos. 8 and 9 shows that the photographic properties are less likely to change in the absence of benzyl alcohol.

Example 2 A color photographic paper was prepared in the same manner as in Example 1 except that the content of bromine ions in the green-sensitive layer emulsion was changed to 80 mol%. As a result of evaluation, the developer of the comparative example showed a large increase in fog with the passage of time, whereas the developer of the present invention showed a small increase in fog with the passage of time and maintained good photographic properties.

Example 3 A color photographic paper prepared in the same manner as in Example 1 was exposed to a wedge shape, and various color developing solutions were subjected to the following processing steps.
A running treatment (continuous treatment) test was performed until the tank was replenished with a volume three times the volume.

The rinse was a three-tank countercurrent system from the rinse.

The formulation of each treatment liquid used is as follows.

Bleach-fix solution (tank solution and replenisher are the same) EDTA ・ Fe (III) NH ₄・ 2H ₂ O 60g EDTA ・ 2Na ・ 2H ₂ O 4g Ammonium thiosulfate (70%) 120ml Sodium sulfite 16g Glacial acetic acid 7g Add water 1000 ml pH 5.5 Rinse solution (tank solution and replenisher are the same) EDTA ・ 2Na ・ 2H ₂ O 0.4 g Water is added 1000 ml pH 7.0 Treatment is performed in the above treatment step using the above treatment solution, The BGR density (stain) in the unexposed area at the end of the running process was measured with a Fuji-type densitometer. In addition, a sample at the end of the running process
After leaving at 80 ° C. (5 to 10 RH) for 1 month, the BGR density of the unexposed area was measured again. The results of changes in the obtained photographic properties are shown in Table 3.

From the results in Table 3, in Experiment Nos. 1 and 2, as a result of the running treatment, the stain was significantly increased, while in Experiment No. 3 to
In 13 it can be seen that the increase in stain is extremely small. In addition, looking at the changes over time after the treatment was completed, Experiment Nos. 3 to 13
In comparison with Experiment Nos. 1 and 2, the increase in stain is very small. From Experiment Nos. 4 to 9, it can be seen that the change with time is particularly reduced in the case of the treatment liquid containing no benzyl alcohol.

Example 4 As described in Table C, the first layer (lowermost layer) to the seventh layer (uppermost layer) were sequentially applied and formed on a double-sided polyethylene laminated paper that had been subjected to corona discharge processing to prepare a printing paper sample.
The preparation of the coating liquid for each layer is as follows. The details of the structural formulas of the coupler, color image stabilizer and the like used in the coating liquid will be described later.

The coating liquid for the first layer was prepared as follows. That is, a mixture of 200 g of a yellow coupler, 93.3 g of an anti-fading agent, 10 g of a high boiling point solvent (p) and 5 g of a solvent (q) and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60 ° C., and then alkanol B (trade name, It was mixed with 3300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of alkylnaphthalene sulfonate (manufactured by DuPont). Next, this solution was emulsified using a colloid mill to prepare a coupler dispersion. From this dispersion, ethyl acetate was distilled off under reduced pressure, and a sensitizing dye for blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole were added to 1400 g of emulsion (Ag
As 96.7g. (Including 170g of gelatin), 1 more
A coating solution was prepared by adding 2600 g of 0% gelatin aqueous solution. The coating solutions for the second layer to the seventh layer were prepared according to the composition of Table C according to the first layer. However, each cyan coupler shown in Table 4 below was used as the cyan coupler of the fifth layer to produce photographic paper.

The following substances were used as sensitizing dyes for the emulsion layers of each layer.

Sensitizing dye for emulsion in blue-sensitive layer; anhydro-5-methoxy-
5'-methyl-3,3'-disulfopropylselenacyanine hydroxide sensitizing dye for the emulsion of the green-sensitive layer; anhydro-9-ethyl-5,
5'-Diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion sensitizing dye; 3,3'diethyl-5-methoxy-9,9 '-(2,2-dimethyl -1,3-Propano) thiadicarbocyanine iodide Also, 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole was used as a stabilizer for each emulsion layer.

Further, as an anti-irradiation dye, 4- (3-carboxy-5-hydroxy-4- (3- (3-carboxy-
5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-di-potassium salt, N,
N '-(4,8-Dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt was used.

In addition, 1,2-bis (vinylsulfonyl) ethane was used as a hardener.

The couplers used are as follows.

Yellow coupler Magenta coupler The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

(Processing step) (Time) (Temperature) Color development 3 minutes 30 seconds 33 ° C Bleach fixing 1 minute 30 seconds 33 ° C Rinse (3 tank cascade) 2 minutes 30 ° C dryness 1 minute 80 ° C On the street.

Color developer Water 800 ml Sodium sulfite Amount shown in Table 4 below N, N'-bis (2-hydroxybenzyl) ethyldiamine-N, N'-diacetic acid 0.1 g Nitrilo-N, N, N-trimethylenephosphone Acid (40%) 1.0 g Potassium bromide 1.0 g Additives C and D shown in Table 4 below Amount shown in Table 4 Potassium carbonate 30 g 4-Amino-3-methyl-N-ethyl-N- [β -(Methanesulfonamido) ethyl] -aniline sulphate 5.5g Optical brightener (4,4'-diaminostilbene type) 1.0g Water was added to 1000ml KOH pH 10.10 Bleach-fixing solution Ammonium thiosulfate (70%) 150 ml Sodium sulfite 15 g EDTA ・ Fe (III) ・ NH ₄・ 2H ₂ O 60 g EDTA 10 g Optical brightener (4,4′-diaminostilbene type) 1.0 g 2-Mercapto-5-amino-3,4-thiadiazole 1.0 g Add water and add 1000 ml of ammonia water to pH 7.0 Rinse solution 5- Rolo-2-methyl-4-isothiazolin-3-one 40 mg 2-Methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-3-one 10 mg Bismuth chloride (40%) 0.5 g Nitrilo-N , N, N-Trimethylenphosphonic acid (40%) 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5g Optical brightener (4,4'-diaminostilber type) 1.0g Ammonia water ( 26%) 2.0 ml of water and 1000 ml of KOH at pH 7.5 In the above treatment, a fresh solution and a part of the color developing solution were allowed to stand for 21 days in the same manner as in Example 1, and then a cyan solution was used. Was measured for Dmin and gradation. Table 4 shows the increase in Dmin and gradation of the aged liquid with respect to the fresh liquid.

Based on the results of Table 4, in comparison with Experiment Nos. 1 to 3, Experiment Nos. 4 to 19
It can be seen that even with the developer left for 21 days, changes in Dmin and gradation are small and the photographic properties are extremely stabilized. In particular, when "C-5" or "C-38" is used as a cyan coupler (Experiment No. 6, 7, 10, 11,
(13, 15, 17 and 18) and that when the concentration of sulfurous acid in the developer is low, the preservative property of the developer is high and the photographic property is more stable (Experiment No. 6, 7 and 10, 11). By comparison).

Example 6 A multilayer color photographic paper was prepared by coating each layer having the composition shown in Table D below on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (a) and color image stabilizer (b)
To 4.4 g, 27.2 cc of ethyl acetate and 7.7 cc of solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 90.0 mol%, Ag 70 g /
(Containing kg), the following blue-sensitive sensitizing dyes are added per 5 mol of silver.
What added ^0x10 <^-4> mol was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer having the composition shown in Table D. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizing dye for each layer.

(5.0 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ^-4 mol per mol of silver halide) (7.0 × 10 ^-5 mol per mol of silver halide) (0.9 × 10 ⁻⁴ mol per mol of silver halide) To the red-sensitive emulsion layer, the following compounds were added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, per mol of silver halide.
5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol and 1.1 × 10 mol, respectively, per mol of silver halide. ^-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(A) Yellow coupler (B) Color image stabilizer (C) solvent (D) Color mixing inhibitor (E) Magenta coupler (F) Color image stabilizer (G) Color image stabilizer (H) solvent (I) UV absorber (J) Color mixing inhibitor (K) Solvent 0 = PO-C ₉ H ₁₉ (iso)) ₃ (l) Cyan coupler (M) Color image stabilizer (N) polymer (O) solvent The above light-sensitive material was exposed through an optical wedge and then processed in the next step.

Processing time Temperature Color development 38 ℃ 1 minute 40 seconds Bleach fixing 30-34 ℃ 1 minute 00 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Rinse 30-34 ℃ 20 seconds Dry 70-80 ℃ 50 Second (3 tank countercurrent system from rinse to) The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g Nitrilotriacetic acid 2.0 g Additive E (see Table 5) 0.04 mol Potassium bromide 0.5 g Potassium carbonate 30g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline sulfate 5.5g N, N-diethylhydroxylamine sulfate 4.0g Optical brightener (UVITEX-CK 1.5g water added 1000ml pH10.25 bleach-fixing agent water 400ml ammonium thiosulfate (70%) 200ml sodium sulfite 20g ethylenediaminetetraacetic acid iron (III) ammonium 60g ethylenediaminetetraacetic acid disodium 10g water 1000ml pH ( 25 ° C) 7.00 Rinse solution Ion-exchanged water (calcium and magnesium are each 3 ppm or less) In the same manner as in Example 5, the change in photographic property after aging was examined. It is shown in Table 5.

According to the present invention, changes in photographic characteristics over time are significantly reduced.

Front page continued (72) Inventor, Ando, No. 210, Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (56) References JP-A-60-35729 (JP, A) JP-A-55-38541 (JP, A) )

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material containing a cyan coupler selected from compounds represented by the following general formula (C-I) or (C-II), containing substantially no benzyl alcohol. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a developer containing an aromatic primary amine color developing agent and a compound represented by the following general formula (I). General formula (I) (In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, R ¹ and R ² may be the same or different, and R ¹ and R ² are linked to each other to form a ring. May be formed.) General formula (CI) (In the formula, R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ⁶ represents an alkyl group or an aryl group. R ⁷ represents a hydrogen atom, a halogen atom,
An alkyl group or an alkoxy group is shown. R ⁷ may combine with R ⁶ to form a ring. Z ¹ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent. ) General formula (C-II) (In the formula, R ⁸ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ⁹ represents an alkyl group having 2 or more carbon atoms. R ¹⁰ represents a hydrogen atom, a halogen atom or an alkyl group. Z ² represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.) 2. Aromatic primary amine color developing agent is 4
The method for processing a silver halide color photographic light-sensitive material according to claim 1, which is a -amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline compound.