JPH077197B2 - 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, and in particular, the stability and light emitting property of a color developer are improved, and continuous processing is performed. The present invention relates to a processing method in which the rise of fog is remarkably reduced.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been used for a long time for forming a color image, and nowadays, it plays a central role in an image forming method for color photography. Plays. However, the color developing solution has a problem that it is easily oxidized by air or metal, and when a color image is formed by using the oxidized developing solution, fog is increased or sensitivity gradation is changed. Therefore, it is well known that desired photographic characteristics cannot be obtained.

Therefore, various means for improving the preservative property of such a color developer have been studied so far, and among them, the method of using hydroxylamine and sulfite ion in combination is the most general.
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 say that it is a desirable homeostasis.

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.
No. 2, No. 56-47038, and aromatic polyhydroxy compounds described in U.S. Pat.No. 3,746,544, hydroxycarbonyl compounds described in U.S. Pat.No. 3615503 and British Patent No. 1306176, JP-A Nos. 52-143020 and 53. -89425 No.
Aminocarbonyl compounds, alkanolamines described in JP-A-54-3532, JP-A-57-44148 and 57-53749
Examples thereof include metal salts described in JP-A No. 52-27638 and hydroxamic acid described in JP-A No. 52-27638. 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, especially the phosphonocarboxylic acids described, and JP-A Nos. 58-195845 and 58.
Compounds described in, for example, No. -203440 and Japanese Patent Publication No. 53-40900 can be mentioned.

(Problems to be Solved by the Invention) However, even if these techniques are used alone or in combination, the fog density of a color image obtained by using a developer after aging due to insufficient preserving performance. However, satisfactory results have not been obtained because the photographic properties may be increased or the photographic performance may be varied, and the developing agents may be competitively acted to inhibit color development.

Furthermore, benzyl alcohol, which is very effective as a color-developing accelerator for color developing agents, has been widely used in the developing solutions for color photographic papers as an almost essential component, but benzyl alcohol is harmful to the environment and hygiene. Since there is a problem such as difficulty in preparing a solution, there is a demand for a technique capable of obtaining sufficient color development even when benzyl alcohol is removed. However, as described above, since many compounds known as preservatives for developing solutions act competitively with the developing agent to cause color inhibition, it is difficult to be compatible with the technique for removing benzyl alcohol as a color accelerator. It was a thing.

Particularly, a color photographic light-sensitive material containing a silver chlorobromide emulsion having a high chlorine content is liable to be inhibited in color development and fog is easily generated during color development (for example, JP-A-58-95345 and JP-A-5-95345).
Therefore, when using such an emulsion, as a preservative that reduces the solubility of the emulsion and has excellent preservative performance, and also enables removal of benzyl alcohol. No satisfactory compound has been found.

Therefore, the object of the present invention is to have excellent stability of a color developer,
Another object of the present invention is to provide a method of processing a silver halide color photographic light-sensitive material in which the increase in fog during continuous processing is significantly reduced.

Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which is excellent in color forming property even though it is processed with a color developing solution which does not substantially contain benzyl alcohol.

(Means for Solving Problems) The above-mentioned objects are to provide a silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the following general formulas (C-I) and (C-II). Processing with a developer containing an aromatic primary amine color developing agent and at least one compound represented by the following general formula (I) and containing sulfite ion of 1.0 g / l or less (including 0). It has been found that this is achieved by a method of processing a silver halide color photographic light-sensitive material characterized by the following.

General formula (C-I) (In the formula, R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₁₂ represents a substituted or unsubstituted R ₁₃ represents a substituted alkyl group or a substituted or unsubstituted aryl group, and R ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.
₁₃ may combine with R ₁₂ to form a ring. Z ₁₁ 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 ₁₄ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₁₅ represents a substituted or unsubstituted Represents an alkyl group having 2 or more carbon atoms.

R ₁₆ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group. Z ₁₂ 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 (I) In the general formula (I), A is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
It represents a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. At this time, A and R may combine to form a ring structure. Y represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

X is -SO ₂ -, or -SO- represent.

According to the present invention, a light-sensitive material containing a cyan coupler represented by the general formulas (C-I) and (C-II) is developed with a sulfite ion of 1.0 g / l or less and a compound of the general formula (I). By treating with a liquid, the stability of the developer can be significantly improved and the occurrence of fog can be prevented.

As described above, certain hydroxamic acids similar to the present compound are already known as preservatives for developing solutions (JP-A-52).
-27638), the compounds of the general formula (I) of the present invention have unexpectedly superior preservative properties than these compounds, and are very effective in that they do not adversely affect the photographic performance obtained. It was found to be.

Even more surprisingly, by incorporating the compound of the general formula (I) of the present invention into the developer, it is still sufficient to remove the development accelerator benzyl alcohol, which was conventionally considered as an essential component, from the developer. It has been found that excellent color development is achieved.

Next, the details of the general formula (I) will be described.

In the general formula (I), A is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, It represents a substituted or unsubstituted aryloxy group. As a substituent,
Halogen atom, aryl group, alkyl group, alkoxy group, aryloxy group, hydroxy group, sulfonyl group,
Sulfonamide group, sulfamoyl group, sulfo group, amide group, ureido group, cyano group, carboxy group, nitro group, amino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic group, (pyridyl group , Morpholino groups, etc.) and the like. Preferably, A is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. At this time, A and R may combine to form a ring structure. The substituent is the same as the substituent mentioned in A. Preferably R is a hydrogen atom.

X is -SO ₂ -, or -SO- represent.

Y represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Specific examples of the case where Y represents a group capable of becoming a hydrogen atom by a hydrolysis reaction include the following.

1) A method of protecting with an ester bond or a urethane bond, that is, Y is Represents Here, examples of R ′ include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted amino group.

2) A method of protecting with an imidomethyl blocking group described in JP-A-57-158638, that is, Y is Represents Where J is And Z represents a plurality of atoms necessary for completing a heterocycle having at least one 5-membered ring or 6-membered ring.

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.

_{I- (2) CH 3 -SO 2} -NH-OH I- (3) CH 3 -SO-NH-OH The compound represented by the compound (I) can be synthesized by a known method shown below.

Organic Functional Group Preparations III P406 to 432 (Academic Press) Synthetic Orgnic Chemistry P419,565,569,576,577 (John Wiley & Sons, Inc.) The compound of the general formula (I) of the present invention is
The content is preferably 0.01 to 50 g, more preferably 0.1 to 20 g.

The color developing solution that can be used in the present invention is 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. The developing agent represented by the following general formula (A) is the general formula (I) of the present invention.
It is particularly preferable because it exhibits further excellent preservability when combined with the compound of (1).

General formula (A) (Where X represents a counter ion of a primary amine) Examples of X include sulfate, hydrochloride, oxalate, phosphate,
Examples thereof include P-toluene sulfonate and nitrate.

Other representative examples are shown below, but the present invention is not limited to these.

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, N-dimethyl-P-phenylenediamine D-8 4-amino-3-methyl-N-ethyl-N-methoxyethyl Aniline D-9 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Putoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, phosphites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is a concentration of about 0.1 g to about 20 g, and more preferably about 0.5 to about 10 g per developing solution.

The color developer used in the present invention preferably contains no hydroxylamine. Even if it contains
The added amount is preferably as small as possible.

Further, it is preferable that benzyl alcohol is not substantially contained from the viewpoint of preventing fog. Substantially free means that the amount of benzyl alcohol per color developer is 2 ml or less, preferably 0 ml.

The present invention is advantageous in that a sufficient color forming property can be achieved without substantially containing benzyl alcohol in the developer.

In addition to the compound of the general formula (I), a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is required as a preservative. Can be added according to The amount added to these color developers is 1.0 g / l or less, preferably 0.5 g / l or less, and the smaller the amount, the more preferable. When the preservative of the present invention is used in a color developer containing no benzyl alcohol,
In terms of preservative and / or photographic characteristics, it is preferable that the amount of sulfite ion added is small.

As other preservatives, hydroxyacetones described in U.S. Patent No. 3,615,503 and British Patent No. 1,306,176, JP-A-5-
2-143020 and 53-89425 α-aminocarbonyl compounds, various metals described in JP-A-57-44148 and 57-53749, various sugars described in JP-A-52-102727 , 52-27638, hydroxamic acids, 59-16014
Α, α′-dicarbonyl compounds described in No. 1, 59-18058
Examples thereof include salicylic acids described in No. 8, alkanolamines described in No. 54-3532, poly (alkyleneimines) described in No. 56-94349, and gluconic acid derivatives described in No. 56-75647. Two or more kinds of these preservatives may be used in combination, if necessary.

In particular, addition of alkanolamines (triethanolasine, diethanolasine, etc.) and / or aromatic polyhydroxy compound is preferable.

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- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 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, 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 in the color developing solution as a precipitation preventing agent for calcium and magnesium, 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 No. 2,227,639. Organic phosphonic acids described, JP-A-52-102726, 53-42730, 54-121127,
Phosphonocarboxylic acids described in JP-A-55-126241 and JP-A-55-659506, and others, JP-A-58-195845 and 58-2034.
Examples thereof include compounds described in JP-B No. 40 and JP-B-53-40900. Specific examples are shown below, but the present invention is not limited thereto.

・ Nitrilotriacetic acid ・ Diethylenetriaminepentaacetic acid ・ Ethylenediaminetetraacetic acid ・ Triethylenetetraminehexaacetic acid ・ N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1, 3-Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotriapropionic acid- 1,2-Diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol ether diaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxy Phenyl acetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-di Acetic acid These chelating agents may be used in combination of two or more as needed. And it may be.

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. As a development accelerator, Japanese Patent Publication No. 37-16
088, 37-5987, 38-7826, 44-12380,
The thioether compounds represented by U.S. Pat. No. 45-9019 and U.S. Pat. No. 3,813,247, and JP-A-52-49829 and U.S. Pat.
No. 15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30074, JP-A-5-
Quaternary ammonium salts represented by 6-156826 and 52-43429, etc., U.S. Pat. Nos. 2,610,122 and 4,119,4
P-Aminophenols described in US Pat. No. 2,494,
903, 3,128,182, 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, U.S. Patent Nos. 2,482,546 and 2,
Amine compounds described in 596,926 and 3,582,346 and the like, Japanese Patent Publication Nos. 37-16088, 42-25201, and U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42-23883, and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, other 1-phenyl-3-pyrazolidones,
Hydrazines, mesoionic compounds, ionic compounds,
Imidazoles and the like can be added as necessary.

If desired, any antifoggant can be added to the color developer used in the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-
Nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole,
Typical examples are nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, hydroxyazaindolidine, 5-nitroindazole and mercaptotriazoles.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. 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 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 amount of replenishment is preferably as small as possible, 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 agent, bleach-fixing solution and fixing solution used in the present invention will be explained.

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 acid of iron (III) (for example, an amino acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid). Polycarboxylic acids, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. The 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, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1, 3-diamino-2-propanol tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine dipropion Acid, phenylenediaminetetraacetic 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 ', N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1, -diphosphonic acid, etc. You can

These compounds may be sodium, potassium, lithium or ammonium salts. Of these compounds, 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 kind of complex salt may be used, or two or more kinds of complex salt may be used, while a ferric salt and a chelating agent are used to form a complex salt in a solution. In that case, one type or two or more types of ferric salts may be used. Furthermore, one or more chelating agents may be used. 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 mol / l.
It is preferably 0.05 to 0.50 mol / l.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent 1,290,8.
No. 12, No. 2,059,988, JP-A No. 53-32736, No. 53-5783
No. 1, No. 53-37418, No. 53-65732, No. 53-72623,
No. 53-95630, No. 53-95631, No. 53-104232, No. 53
-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; JP-B-45-8506, JP-A-52-20832,
No. 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, iodide described in JP-A-58-16235; polyethylene described in West German Patents 966,410, 2,748,430. Oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434
No. 49-58644, No. 53-94927, No. 54-35727,
The compounds described in JP-A-55-26506 and JP-A-58-163940, iodine, bromide ion and the like can be mentioned. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of large accelerated curing, and particularly, US Patent 3,893,
Compounds described in 858, West German Patent 1,290,812 and JP-A-53-95630 are preferable.

In addition, the bleaching solution or bleach-fixing solution used in the present invention contains a bromide (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-1,8
A thioether compound such as 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.

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 to 10
Is preferable, and 5-9 is particularly 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 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.

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

The bleach-fixing solution and fixing solution in the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, bisulfite) as preservatives. Potassium, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound. These compounds are about 0.02 ~
It is preferable to contain 0.50 mol / l, more preferably
It is 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

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

Next, the water washing step in the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" may be used without providing a substantial water washing step in place of the usual "water washing treatment". As described above, the “water washing treatment” in the present invention is used in a broad sense as described above. In addition, the term “rinsing treatment” as used herein includes rinsing treatment and other alternative washing treatments.

The amount of washing water in the present invention is difficult to define because it depends on the number of multi-stage countercurrent washing baths and the carry-in amount of the pre-bath component of the light-sensitive material, but in the present invention, bleaching and fixing in the final washing bath are performed. The liquid component should be 1 × 10 ⁻⁴ or less. For example, in the case of 3 tank countercurrent washing, about 1000 per 1 m ² of light-sensitive material
It is preferable to use at least ml, and more preferably at least 5000 ml. In the case of water-saving treatment, it is 10 per 1 m ² of light-sensitive material.
It is recommended to use 0-1000 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 And Anti-Fungal Agents "(J.Antibact.Antifung.Agents), Vol.11, No.
5, compounds described in p207 to 223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antiprohibition and Antifungal", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, and dried sardines. If necessary, a surfactant or the like for preventing load and unevenness can be added. Or West, “Photographic Science and Engineering Magazine (Phot.Sci.En
g.), Vol. 6, pp. 344-359 (1965), etc. may be added.

Add chelating agents, bactericides and anti-bacterial agents to the wash water,
The present invention is particularly effective in the case where the amount of washing water is greatly reduced by multi-stage countercurrent washing with two or more tanks. It is also particularly effective when a multi-stage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the usual water washing step. In these cases, the bleaching and fixing components in the final bath may be 5 × 10 ^-2 or less, preferably 1 × 10 ^-2 or less.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjust membrane pH (eg pH 3-8)
Various buffers for (eg borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Typical examples include aldehydes such as polycarboxylic acid used in combination) and formalin.
In addition, 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.), surfactant, fluorescent brightener,
Various additives such as a hardener 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 as a film pH adjusting agent for the processor in order to improve the image storability.

When the amount of washing water as described above is significantly reduced, it is preferable 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 a pre-bath for the purpose of reducing the amount of drainage.

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 stirring, air stirring 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.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride, but in the case of performing rapid processing or low replenishment processing. In particular, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol% is particularly preferable. The processing method of the present invention is further characterized in that even if an emulsion having a high silver chloride content is used, the occurrence of fog is sufficiently suppressed, and that color development is not inhibited. When high sensitivity is required and fog during production, storage, and / or processing is required to be particularly low, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide or an odor is used. A silver halide emulsion 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 development accelerators such as a silver halide solution, a fogging agent, and a developer described below to act during processing. The use of is capable of speeding up the development to some extent without being limited by the content of silver bromide, which is preferable in some cases. In any case, it is not preferable to contain a large amount of silver iodide, and the amount may be 3 mol% or less. These silver halide emulsions are preferably used mainly for color paper and the like. For color photosensitive materials for photography (negative film, reversal film, etc.),
Silver iodobromide and silver chloroiodobromide are preferred, and the silver iodide content is preferably 3 to 15 mol%.

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 is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. In the above case, the value is also expressed in terms of sphere. 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. Furthermore, 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, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a 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 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, Paul Montel, 1967], Duffin, "Photoemulsion Chemistry" [GF Duffin, Photograhic Emulsion Ch
emistry, Focal Press, 1966], "Production and coating of photographic emulsions" by Zelikman et al. [VL Zelikman et al, Making.
and Coating Potographic Emulsion, published by Focal Press, 196
4 years] 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 form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, 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, which includes a step of converting already formed silver halide into a silver halide having a smaller solubility product until the completion of the silver halide grain formation step, and a halogenated 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, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

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 No. 54-155828, etc. are precipitated, physically aged,
It can be used in chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method or ultrafiltration method 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, rhodanines); 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, and Fe, 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 used in 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, 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 nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, benzimidazole A nucleus, a quinoline nucleus, etc. 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 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.

Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect by itself, a substance that does not substantially absorb visible light, or a substance that exhibits 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 particularly useful to apply them to grains having a high silver bromide or silver iodide content 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 coupler or Japanese Patent Publication No. 55-10739, 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.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, 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 US 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 U.S. Patent 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 compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

The cyan coupler that can be used in the present invention is a cyan coupler represented by the following general formulas (C-I) and (C-II). By using at least one of the cyan couplers, good fog can be obtained with less fog. Such an effect is remarkable.

In the present invention, in addition to the cyan couplers represented by the above general formulas (CI) and (C-II), oil protect type naphthol type and phenol type couplers may be contained.

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

General formula (C-I) (In the formula, R ₁₁ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ₁₂ represents an alkyl group or an aryl group. R ₁₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. And R ₁₃
May combine with R ₁₂ to form a ring. Z ₁₁ 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 ₁₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₁₅ represents an alkyl group having 2 or more carbon atoms. R ₁₆ represents a hydrogen atom, a halogen atom or an alkyl group. Z ₁₂ represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine type color developing agent.) Cyan couplers represented by the general formulas (C-I) and (C-II) In R ₁₁ , R ₁₂ and R ₁₄ as the alkyl group having 1 to 32 carbon atoms, for example, a methyl group, a butyl group, a tridecyl group,
Examples thereof include a cyclohexyl group and an allyl group, examples of the aryl group include a phenyl group and naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-pyridyl group.
Examples thereof include an imidazolyl group, a 2-furyl group and a 6-quinolyl group. These groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group,
2-methoxyethoxy group etc.), aryloxy group (eg 2,4-di-tert-aluminphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group etc.), alkenyloxy group (eg 2-propenyloxy group) Groups), acyl groups (eg acetyl group, benzoyl group etc.), ester groups (eg butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group etc.), amide groups (Eg, acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group, etc.), carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, tylsulfamoyl group, etc.), imide group , (For example, Amide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (For example, an ethylthio group, a phenylthio group, etc.), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like may be substituted.

The amino group of R ₁₁ 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 ₁₁ include an anilino group and a benzothiazolylamino group.

In the general formula (CI), when R ₁₃ is a substitutable substituent, it may be substituted with the optionally substituted substituent described for R ₁₁ .

The carbon number of R _{15 in} the general formula (C-II) is at least 2
As the alkyl group which may be substituted, for example,
Ethyl group, propyl group, butyl group, pentadecyl group, te
Examples thereof include rt-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group and methoxymethyl group.

In the general formula (CI) and general formula (C-II), Z ₁₁
And Z ₁₂ each represent a hydrogen atom or a coupling-off group (including a coupling-off atom; the same applies hereinafter), and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkoxy. Group (for example, 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.), amide group (eg, dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxy Carbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyl group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (eg, , Ethylthio group, a phenylthio group,
A tetrazolylthio group), an imide group (eg, a succinimide group, a hydantoinyl group, etc.), an aromatic azo group (eg, a 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 ₁₁ 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 ₁₃ and R ₁₂ do not form a group, R ₁₂ is preferably a substituted or unsubstituted alkyl group or an aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. , R ₁₃ is preferably a hydrogen atom.

In formula (C-II), R ₁₄ 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 ₁₅ has 2 to ₁₅ carbon atoms.
Is an alkyl group and a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group or an alkyloxy group.

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

Preferred R ₁₆ in the general formula (C-II) is a hydrogen atom or a halogen atom, with a chlorine atom and a fluorine atom being particularly preferred.

Preferred Z in the general formulas (C-I) and (C-II)
₁₁ and Z ₁₂ 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 ₁₂ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In formula (CI), Z ₁₁ 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 couplers represented by the general formulas (C-I) and (C-II) can be synthesized based on the descriptions in JP-A-59-166956 and JP-B-49-11572.

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. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. 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, and the same compound can be used in two or more different layers. Can also 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. 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,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-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 citrate, etc.), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary tablet, a boiling point of about 30 ° C. or higher, preferably an organic solvent of 50 ° C. or higher and about 160 ° C. or lower can be used,
Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-
Examples include ethoxyethyl acetate and dimethylformamide.

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 light-sensitive material used in the present invention is, as a color antifoggant or a color mixture 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 derivative, etc. May be included.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Representative examples thereof include ethers or ester derivatives obtained by silylated and alkylating the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines, and these compounds. 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 light-sensitive material layer structure of a normal color paper, either one layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer,
An ultraviolet absorber is preferably contained 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. The protective layer may contain a matting agent having an arbitrary particle size.

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

The light-sensitive material used in 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. Oxonol-based, anthraquinone-based, or azo-based dyes are preferred. Oxonol dyes that absorb green light and red light are particularly preferable.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, stilbene-based, triazine-based,
A whitening agent such as an oxazole type or a coumarin type may be included. 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. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
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 photosensitivity.

The light-sensitive material used in the present invention 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.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material used in 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, etc .; sugar derivatives such as sodium alginate and starch derivatives;
Use various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. be able to. The use of acrylic acid modified polyvinyl alcohol in the protective layer is particularly useful, and even more useful for rapid processing with silver chloride emulsions.

As gelatin, in addition to 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 used in the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof as described above, lubricants and mordants are further added. , Matting agents, antistatic agents, plasticizers,
Alternatively, various additives useful for photographic light-sensitive materials may be added. Representative examples of these additives are Research Disclosure 17643 (December 1978) and 18716.
(November 1979).

These additives are very important in rapid printing, rapid processing, and further in relation to the compound of the general formula [I] of the present invention. Further, particularly when the halogen composition of the emulsion to be used contains a high content of silver chloride, it is useful in the present invention in combination with a mercaptoazole-based, mercaptothiadiazole-based, and mercaptobenzazole-based compound in color formation and fog generation. is there.

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, polyester film of cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

(Example) Below, the effect of this invention is demonstrated in an Example.

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) 19.1 g and color image stabilizer (b) 4.4
To g, 27.2 ml of ethyl acetate and 7.9 ml of the solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 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 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 5.0 × 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 A 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 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 each emulsion.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

(J) Solvent (iso C ₉ H ₁₉ O ₃ P = 0 The obtained color photographic paper was processed in the following processing steps in which the composition of the color developing solution was changed.

Processing process Temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Rinse 1 35 ℃ 20 seconds Rinse 2 35 ℃ 20 seconds Rinse 3 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Rinse 3 to rinse 1 tank It was washed with countercurrent water. The treatment liquids used are as follows. Color developer additive See Table 1 Benzyl alcohol See Table 1 Diethylene glycol See Table 1 Sodium sulfite 0.2g Potassium carbonate 30g EDTA ・ 2Na 1g Sodium chloride 1.5g Color developing agent 0.012mol Whitening agent (4,4'-diamino added stilbene) 3.0 g water to 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%) 120 ml sodium sulfite 16g glacial acetic acid 7g water added 1000 ml pH 5.5 Rinse solution Formalin (37%) 0.1 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.6 ml Bismuth chloride 0.35 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g EDTA・ 4H 0.5g Sodium sulfite 1.0g 5-Chloro-2-methyl-4-50mg Isothiazolin-3-one Water was added to 1000ml Color developer for each composition immediately after preparation (new After standing for 14 days at 40 ° C. After the liquid) and liquid preparation of 2 kinds of (aging solution) was used.

Table 1 shows the photographic characteristics of the obtained fresh liquid and aged liquid.

The photographic property is represented 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.

If there is no preservative or if it is hydroxylamine, fog will occur over time and the gradation will change (No.1.2.3). Furthermore, when hydroxylamine is used, it can be seen that benzyl alcohol cannot be removed because the gradation is low and the color development is inhibited in a system in which benzyl alcohol is not present (No. 1).

On the other hand, in the present invention, the generation of fog and the change in photographic property with time are small, and particularly when the developing agent D is used, a better result is shown.

Furthermore, it can be seen that the developer according to the present invention from which benzyl alcohol has been removed is superior in stability over time in terms of both Dmin and gradation (No. 9.11 and 13).

Example 2 In Example 1, the bromine ion content of the green-sensitive layer emulsion was adjusted to 80%.
The change in photographic property with the passage of time was evaluated in the same manner as in Example 1 with mol% being set, and in the constitution of the present invention, good results were obtained with little increase in fog.

Example 3 As described in Table B, the first layer (bottom layer) to the seventh layer (top layer) were applied to double-sided polyethylene laminated paper that had been subjected to corona discharge machining to prepare a sample.

The coating liquid for the first layer was prepared as follows. Yellow coupler 200g, anti-fading agent 93.3g, high boiling point solvent (p) 10g and (q) 5g, ethyl acetate 6 as an auxiliary solvent
The mixture containing 00 ml was heated and dissolved at 60 ° C, and then alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont)
Was mixed with 3,300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of and was emulsified by using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from this dispersion under reduced pressure, and 1,400 g (as Ag) of an emulsion containing a blue-sensitive emulsion layer sensitizing dye and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole was added. 96.7 g and 170 g of gelatin) were added, and 2,600 g of 10% gelatin aqueous solution was further added to prepare a coating solution. The coating solutions for the second to seventh layers were prepared according to the first layer.

The following sensitizing dyes were used in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3 ′ -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3′-diethyl-5-methoxy-9,9 ′-(2,2-dimethyl-1,3-propano) thiadicarbocyanine iodide The following was used as a stabilizer for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-1,
3,4-Triazole The following substances were used as anti-irradiation dyes.

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

The couplers used are as follows.

The cyan coupler was modified as shown in Table 2.

The compounds used in this example are as follows.

UV absorber (n): 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole UV absorber (o): 2- (2-hydroxy-3,5-di-tert-butyl) Phenyl) benzotriazole Solvent (p): Di (2-ethylhexyl) phthalate Solvent (q): Dibutylphthalate Anti-fading agent (r): 2,5-di-tert-amylphenyl-3,5-di-tert-butyl Hydroxybenzoate Anti-color mixing agent (s): 2,5-di-tert-octylhydroquinone Anti-fading agent (t): 1,4-di-tert-amyl-2,5-dioctyloxybenzene Anti-fading agent (u): 2,2'-Methylenebis- (4-methyl-6-tert-butylphenol) The multilayer color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Processing time Temperature Color development 3 minutes 30 seconds 33 ° C Bleaching fixing 1 minute 30 seconds 33 ° C Rinse (3 tanks 2 minutes 30 ° C cascade) Drying 1 minute 80 ° C The processing solutions used are as follows.

Color developer Water 800 ml Triethanolamine 10 ml 5,6-Dihydroxy-1,2,4-benzene sodium trisulfonate 300 mg N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid 0.1g Nitrilo-N, N, N-trimethylenephosphonic acid (40%) 1.0g Potassium bromide 0.6g Additives Table 2 Sodium sulfite Table 2 Potassium carbonate 30g N-Ethyl-N- (β-methanesulfonamidoethyl) ) -3-Methyl-4-aminoaniline sulphate 5.5g Fluorescent brightener (4,4'-diaminostilbene type) 1.0g Add water and add 1000ml KOH pH 10.10 Bleach-fixing solution Ammonium thiosulfate (70% ) 150 ml Sodium sulfite 15 g Ethylenediamineiron (III) ammonium 60 g Ethylenediaminetetraacetic acid 10 g Fluorescent brightener (4,4'-diaminostilbene type) 1.0 g 2-Mercapto-5-amino-3,4- Asiazol 1.0 g Water is added to 1000 ml with ammonia water pH 7.0 Rinsing solution 5-chloro-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-trimethylene phosphonic acid (40%) 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.5 g Fluorescent whitening agent (4,4'-diaminostilbene type) 1.0g Ammonia water (26%) 2.0ml Add water to 1000ml KOH pH7.5 Color developer for each composition immediately after preparation Two types were used (a fresh liquid) and after 20 days at 38 ° C. after preparation (after aging).

The Dmin and gradation of cyan in the fresh liquid and the aged liquid were determined, and the difference between the results obtained with the aged liquid and the fresh liquid is shown in Table 2.

As is clear from Table 2, when treated with the treatment liquid of the present invention, the increase in fog was small even when the aged liquid was used,
It can be seen that there is little change in gradation. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

On the other hand, in the case of processing with a processing solution to which hydroxylamine is added, there is a large increase in fog with the passage of time of the color developing solution and a large change in gradation.

When a light-sensitive material containing a cyan coupler represented by the general formula (C-I) or (C-II) is processed with the processing solution of the present invention, the general formulas (C-I) and (C-II) are used. )
It can be seen that, compared with the case of processing a light-sensitive material containing a cyan coupler other than the above, the increase in fog with time of the color developing solution is small and the gradation change is small. Further, this effect is more remarkable when the concentration of sulfite ion in the treatment liquid is low.

Example 4 Using the color photographic paper obtained in Example 1, a running test was conducted until the tank capacity (60 l) of the color developing solution was replenished by 3 times in the following processing steps.

However, the composition of the color developing solution was changed as shown in Table 3.

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

The composition of each treatment liquid used is as follows.

Bleach-fixing solution (tank solution and replenisher are the _{same) EDTAFe (III) NH 4 ·} 2H 2 O 60g EDTA · 2Na · 2H 2 O 4g Ammonium thiosulfate (70%) was added to 120ml sodium sulfite 16g glacial acetic 7g water 1000 ml pH 5.5 Rinse solution (tank solution and replenisher are the same) EDTA ・ 2Na ・ 2H ₂ O 0.4g Water is added and 1000ml pH 7.0 Treatment is performed by the above treatment method, and B of the end-exposure part at the start of running and at the end of running ( The blue, G (green) and R (red) densities were measured with a Fuji type self-recording densitometer. Furthermore, the sample at the end of running is 60 ℃
After leaving it under 70% RH for 2 months, B of the last exposed part,
The G and R concentrations were measured.

The results obtained are shown in Table 3.

From Table 3, when the hydroxylamine was added, the increase in fog after running was large, whereas when the treatment liquid of the present invention was used, the increase in fog after running was small and the time-dependent stain after processing was increased. Is also suppressed.

This effect is particularly remarkable when running in the treatment liquid containing no benzyl alcohol.

Example 5 Compound I used in Experiment Nos. 19 and 28 of Example 1
Instead of-(6), I- (1), I- (8), I- (17), I- (22), I
-(29), I- (36), I- (43), and I- (50) were used, but the same experiment was carried out except that the same results as in Example 1 were obtained.

(Effects of the Invention) The present invention significantly improves the stability and color developability of a color developing solution, and as a result, even in a processing method using a color developing solution after a lapse of time, a fog increase and a gradation change are significantly suppressed. To give a color image with excellent photographic properties.

Such effects of the present invention were particularly remarkable in a color developer which does not substantially contain benzyl alcohol, which has a high pollution load.

Further, such an effect of the present invention was more remarkable when the concentration of sulfite ion in the treatment liquid was low. Furthermore, the effect of the present invention was remarkable when a light-sensitive material containing a specific cyan coupler was processed.

Further, even in the continuous processing, the increase in fog was remarkably reduced, and the stability of the obtained color image with time was excellent.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material containing at least one of cyan couplers represented by the following general formulas (C-I) and (C-II), and an aromatic primary amine color developing agent and A silver halide color photograph characterized by being treated with a developer containing at least one compound represented by the following general formula (I) and containing sulfite ion of 1.0 g / l or less (including 0). Method of processing photosensitive material. General formula (C-I) (In the formula, R ₁₁ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₁₂ represents a substituted or unsubstituted R ₁₃ represents a substituted alkyl group or a substituted or unsubstituted aryl group, and R ₁₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.
₁₃ may combine with R ₁₂ to form a ring. Z ₁₁ 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 ₁₄ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₁₅ represents a substituted or unsubstituted R ₁₆ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group, Z ₁₂ represents a hydrogen atom, a halogen atom or an aromatic primary amine type color developing agent. A group capable of splitting off upon reaction with an oxidant is shown.) General formula (I) (In the general formula (I), A is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted An alkoxy group of
Alternatively, it represents a substituted or unsubstituted aryloxy group.
R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. At this time, A and R may combine to form a ring structure. Y is
It represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction. X is Represents or -SO- - -SO _2. ) 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the aromatic primary amine color developing agent is a compound having the following general formula (A). General formula (A) (Where X represents the counterion of the primary amine) 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developing solution contains substantially no benzyl alcohol.