JPH07120000B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing an exposed silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material), and in particular, it is sufficiently removed in a short time. The present invention relates to an improved processing method capable of performing silver and having excellent photographic properties.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color developing step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the next desilvering process,
The action of an oxidizing agent (commonly called a bleaching agent) oxidizes the silver produced in the color development step, and then it is dissolved by a complexing agent of silver ions, which is commonly called a fixing agent. Through the desilvering process, only a dye image is formed on the color light-sensitive material.

The above desilvering step is carried out in two baths of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, and in one bathing with a bleaching fixing bath in which a bleaching agent and a fixing agent are coexisted. There is.

In addition to the above-mentioned basic steps, the actual development processing includes various auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like.

In the present invention, the bath having a bleaching ability refers to both the bleaching bath and the bleach-fixing bath, and examples of the bleaching agent used in these baths having a bleaching ability include red blood salt, dichromate, and chloride chloride. Diiron, ferric aminopolycarboxylic acid complex salts, persulfates and the like are known.

However, red blood salts and dichromates have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Further, ferric chloride has various problems in practical use due to problems such as generation of iron hydroxide and generation of stains in the subsequent water washing step. Persulfate has the disadvantage that it has a very weak bleaching action and requires a remarkably long bleaching time. Regarding this, a method of increasing the bleaching action by using a bleaching accelerator together has been proposed, but persulfate itself is regulated by the Fire Service Act as a dangerous substance, and various measures for storage are required. There are drawbacks.

Aminopolycarboxylic acid ferric iron complex salt is the most widely used bleaching agent at present because it has few pollution problems and no storage problems like persulfate. As an aminopolycarboxylic acid ferric complex salt, an extremely large number of compounds are known, but from the viewpoints of bleaching ability, cost, etc., ethylenediaminetetraacetic acid ferric complex salt, diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediaminetetraacetic acid. Ferric complex salts have been used as preferred compounds.

However, the bleaching power of conventionally used ferric ethylenediaminetetraacetic acid complex salts and diethylenetriaminepentaacetic acid ferric iron complex salts is not always sufficient, and those using this as a bleaching agent are mainly composed of silver chlorobromide emulsions. In the case of bleaching or bleach-fixing the low-sensitivity silver halide color light-sensitive material described above, the desired purpose can be achieved for a while, but silver chlorobromoiodide or silver iodobromide emulsion is mainly used and When processing a sensitized and high-sensitivity color light-sensitive material, especially a color reversal light-sensitive material for photographing and a color negative light-sensitive material for photographing using a high silver content emulsion, desilvering failure occurs or it takes a long time to bleach. Has the drawback of requiring

As a method of improving such a drawback of the ferric aminopolycarboxylic acid complex salt, a method of adding various bleaching accelerators to a bath having a bleaching ability or a prebath thereof has been proposed.

For example, U.S. Pat.No. 3,893,858, British Patent No. 13884
2, various mercapto compounds as described in JP-A-53-141623, compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854 Thiazolidine derivatives as described in JP-A-53-94927, Isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506, JP-B-49-26
Examples include thiourea derivatives as described in JP 586, thioamide compounds as described in JP-A-49-42349, and dithiocarbamate salts as described in JP-A-55-26506. To be

Some of these bleaching accelerators have a bleaching promoting effect to some extent.
The oxidizing power of iron complex salt, diethylenetriaminepentaacetic acid ferric iron complex salt, cyclohexanediaminetetraacetic acid ferric iron complex salt, etc. is basically weak, and the effect obtained by the bleaching accelerator does not meet the recent demand for rapid treatment in the industry. .

Further, as another means for increasing the bleaching power of the ferric aminopolycarboxylic acid complex, it is known to lower the pH of a solution having a bleaching ability, but it causes a problem that the cyan dye causes defective color restoration.

As another means, among aminopolycarboxylic acids, compounds having a low stability constant with ferric iron have a high bleaching ability, and, for example, 1,3-diaminopropanetetraacetic acid described in JP-A-62-222252. A ferric complex salt and a 1,2-diaminopropanetetraacetic acid ferric complex salt are known, but it has been found that these compounds also have a serious problem.

That is, when the processing is performed with a solution having a bleaching ability containing these ferric complex salts subsequent to color development, remarkable bleaching fog occurs in the light-sensitive material, and good processing performance cannot be obtained.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a processing method for achieving speeding up of bleaching without causing bleaching fog, and a second object of the present invention is to prevent defective color restoration. It is an object of the present invention to provide a processing method which achieves quickening of bleaching without occurring. A third object is to provide a rapid processing method without environmental pollution or handling danger.

(Means for Solving the Problem) The above object of the present invention was selected from the ferric complex salts of the following (1) to (7) following color development processing of the exposed silver halide color photographic light-sensitive material. Halogenation characterized by introducing into a bleaching solution having a pH of 5.0 to 4.0 containing at least one kind, and within 15 seconds after that, jetting the bleaching solution against the emulsion surface of the light-sensitive material for processing. It was achieved by the processing method of silver color photographic light-sensitive material.

(1) 1,2-Diaminopropanetetraacetic acid ferric iron complex salt (2) 1,3-Diaminopropanetetraacetic acid ferric iron complex salt (3) 1,4-Diaminobutanetetraacetic acid ferric iron complex salt (4) 1, 5-Diaminopentanetetraacetic acid ferric iron complex salt (5) Glycol ether diaminetetraacetic acid ferric iron complex salt (6) Iminodiacetic acid ferric iron complex salt (7) N-methyliminodiacetic acid ferric iron complex salt In the present invention, a bleaching solution. The ferric iron complex salt according to any one of (1) to (7) above (hereinafter referred to as the ferric iron complex salt of the present invention).
The amount is 0.05 mol to 1 mol per 1 mol.

In the above preferable range, bleaching proceeds more rapidly, and defective color restoration and bleaching fog are less likely to occur.

The present invention is carried out in a bleaching solution having a pH of 5.0 or less. By setting the pH to 5.0 or less, the bleaching speed is remarkably improved and bleaching fog can be suppressed. However, if the pH is lowered too much, the ferric complex salt of the present invention will precipitate.

Usually, when the pH is lowered, the cyan dye causes a color recovery failure, so it was the conventional wisdom to keep the color density at 5.5 or more. The amazing effect that a perfect bleaching is achieved can be obtained.

In the present invention, the introduction into the bleaching solution after the color developing treatment means that the light-sensitive material is directly immersed in the bleaching solution after the color developing treatment without any treatment with other solutions. By performing the bleaching treatment without passing through another liquid in this way, it is possible to save time and facilitate the achievement of rapid treatment.

In the present invention, the light-sensitive material after color development is processed in a bleaching solution while making a jet stream of the bleaching solution collide with the emulsion surface. The jet of bleaching solution sucks the bleaching solution with a pump,
It can be generated by ejecting toward the emulsion surface from a nozzle provided at a position facing the emulsion surface. More specifically, JP-A-62-183460, page 3, lower right column to page 4, lower right column, pumps from a slit or nozzle provided facing the emulsion surface described in the section of Examples of the invention. A method of discharging the liquid that has been pressure-fed can be adopted. The jet speed at the time of colliding with the emulsion surface is preferably as large as possible within a range that does not hinder the conveyance of the photosensitive material in the automatic processor, specifically, 0.3 m to 3 m per second.
Is preferred.

In the present invention, the light-sensitive material is introduced into the bleaching solution, and then 15
The impingement of the jet within a second means the time from when a point on the photosensitive material comes into contact with the liquid until the same point hits the center point of the first jet, and this time is within 15 seconds. By so doing, the color developer retained in the emulsion film is diffused early and bleach fog is prevented from occurring. In addition, the bleaching solution rapidly penetrates into the emulsion film, and the bleaching ability of the ferric complex salt of the present invention is fully exhibited, resulting in extremely rapid bleaching. Therefore, it is preferable that the time for receiving the jet flow collision after introduction into the bleaching solution is as short as possible, specifically within 10 seconds, and particularly preferably within 5 seconds. The bleaching promoting effect by jet collision is extremely small in the conventionally used ferric ethylenediaminetetraacetic acid complex salt and the like, and it is unexpectedly not expected that the ferric complex salt of the present invention has a particularly large effect. there were.

In the present invention having such a constitution, as a ferric iron complex salt that particularly effectively achieves speeding up of bleaching, bleaching fog, and prevention of color restoration failure, 1,3-diaminopropanetetraacetic acid ferric iron complex salt is used. Most preferred, and then ferric 1,4-diaminobutanetetraacetic acid ferric complex and N-methyliminodiacetic acid secondary
Iron complex salts are preferred.

Further, the bleaching bath of the present invention may further contain other ferric iron complex salt of aminopolycarboxylic acid depending on its purpose.

Bleaching fog can be further prevented by using, for example, a ferric ethylenediaminetetraacetic acid ferric complex salt, a diethylenetriaminepentaacetic acid ferric iron complex salt, and a cyclohexanediaminetetraacetic acid ferric iron complex salt. These ferric iron complex salts are used in 1/5 to 2 times the molar ratio of the ferric iron complex salt of the present invention.

In addition to the above compounds, the bleaching bath of the present invention contains a rehalogenating agent such as a bromide such as potassium bromide, sodium bromide, ammonium bromide or a chloride such as potassium chloride, sodium chloride or ammonium chloride. You can In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
Additives known to be commonly used in bleaching solutions, such as one or more inorganic acids having pH buffering ability such as tartaric acid, organic acids and salts thereof, can be added.

The bleaching solution of the present invention preferably contains a bleaching accelerator.

The present inventors have found that the effect of the bleaching accelerator is exerted in a more enlarged manner in combination with the jet impingement of the present invention.

As these bleaching accelerators, the following general formulas (I) to (VI
Those represented by II) are preferred.

General formula (I) Here, A is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group, and (when n = 1, A represents a simple aliphatic group, aromatic group, or heterocyclic group). The aliphatic linking group represented by is an alkylene group having 3 to 12 carbon atoms (eg, trimethylene, hexamethylene,
Cyclohexylene and the like).

Examples of the aromatic linking group include arylene groups having 6 to 18 carbon atoms (for example, phenylene, naphthalene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group (eg, thiophene, butene, triazine, pyridine, piperidine, etc.) composed of one or more heteroatoms (eg, oxygen atom, sulfur atom, nitrogen atom).

Here, the aliphatic linking group, aromatic linking group, and heterocyclic linking group are usually one, but two or more may be linked, and the linking form may be direct or a divalent linking group (for example,- O
-, -S-, It may be —SO ₂ —, —CO— or a linking group that can be formed from these linking groups, and R ⁵ represents a lower alkyl group. ).

Further, the aliphatic aromatic group, aromatic linking group and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

X is -O-, -S-, (Wherein R ⁴ represents a lower alkyl group (eg, methyl group, ethyl group, etc.)), R ¹ and R ² represent a substituted or unsubstituted lower alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group). Group, a pentyl group, etc., and the substituents include a hydroxy group, a lower alkoxy group (eg, methoxy group, methoxyethoxy group, hydroxynitoxy group, etc.), an amino group (eg, unsubstituted amino group, dimethylamino group). , N-hydroxyethyl-N-methylamino group) are preferred. Here, when there are two or more substituents, they may be the same or different.

R ³ represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.),
Y is an anion (halide ion R ¹ (or R ² )) and A is a carbon atom or a hetero atom (eg oxygen atom, nitrogen atom,
And a 5-membered or 6-membered heterocycle (eg, hydroxyquinoline ring, hydroxyindole ring, isoindoline ring, etc.) may be formed.

Further, R ¹ (or R ² ) and R ³ are linked via a carbon atom or a hetero atom (for example, an oxygen atom, a nitrogen atom, a sulfur atom), and a 5-membered or 6-membered hetero ring (for example, a piperidine ring, Pyrrolidine ring, morpholine ring, etc.) may be formed.

l represents 0 or 1, m represents 0 or 1, n represents 1, 2 or 3, p represents 0 or 1, and q represents 0, 1, 2 or 3.

General formula (II) In the formula, R ₁ and R ₂ may be the same or different and each is a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, particularly preferably a methyl group, an ethyl group or a propyl group) or an acyl group. Represents a group (preferably having a carbon number of 1 to 3, such as an acetyl group and a propionyl group), and n is an integer of 1 to 3.

R ₁ and R ₂ may combine with each other to form a ring.

As R ₁ and R ₂ , a substituted or unsubstituted lower alkyl group is particularly preferable.

Here, examples of the substituents possessed by R ₁ and R ₂ include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (III) In the formula, R ₃ and R ₄ have the same meanings as R ₁ and R _{2 in} formula (I). n
Is an integer of 1 to 3.

R ₃ and R ₄ may combine with each other to form a ring.

As R ₃ and R ₄ , a substituted or unsubstituted lower alkyl group is particularly preferable.

Here, examples of the substituents possessed by R ₃ and R ₄ include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

In the formula, R ₅ is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, especially a methyl group, an ethyl group, propyl). Group is preferred) and an amino group having an alkyl group (such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group).

Here, examples of the substituent that R ₅ has include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and the like.

General formula (VII) In the formula, R ₆ and R ₇ may be the same or different and each is a hydrogen atom or an alkyl group which may have a substituent (preferably a lower alkyl group such as a methyl group, an ethyl group or a propyl group), A phenyl group which may have a substituent or a heterocyclic group which may have a substituent (more specifically, a heterocyclic ring containing at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom). A pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazole ring, a benzotriazole ring, a thiazole ring, an imidazole ring, etc.), and R ₆ is a hydrogen atom or a lower alkyl group which may have a substituent (for example, Methyl group, ethyl group, etc., preferably having 1 to 3 carbon atoms.

Here, examples of the substituents possessed by R _{6 to} R ₈ include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and a lower alkyl group.

R ₉ represents a hydrogen atom or a carboxyl group.

General formula (VIII) In the formula, R ₁₀ , R ₁₁ , and R ₁₂ may be the same or different and each represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably 1 to 3 carbon atoms).

R ₁₀ and R ₁₁ or R ₁₂ may combine with each other to form a ring.

X is a substituent (eg, a lower alkyl group such as a methyl group,
(Alkoxyalkyl groups such as acetoxymethyl group)
Represents an amino group, a sulfonic acid group or a carboxyl group which may have

R _{10 to} R ₁₂ are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X is preferably an amino group or a dialkylamino group.

The general formulas (I) to (VI which can be used in the present invention are described below.
Specific compounds represented by II) are described below, but the invention is not limited thereto.

The compound of the general formula (I) can be synthesized by a method well known in the following documents.

U.S. Pat.No. 4,552,834, Japanese Patent Publication No. 54-12,056, Japanese Patent Laid-Open No. 51
-192,953 issue.

Although any of the above compounds can be synthesized by a known method, particularly for the compound of the general formula (II), US Pat.
5,984, G. Schwarzenbach et al., Helv.Chim.Ac
ta., 38 , 1147 (19555), ROClinton et al., J. Am. Che
m.Soc., 70, 950 (1948 ), the general formula (III) compound-53-95630 discloses for the general formula (IV), the compounds of (V) is, JP 54-52534 Publication, general formula (VI)
For the compounds described in JP-A-51-68568 and JP-A-51-70763.
No. 53-50169, Japanese Patent Publication No. 53-9854, Japanese Patent Application No. 58-88938, for compounds of the general formula (VII).
For the compound of general formula (VIII), reference can be made to JP-A-53-94927.

A compound having a mercapto group or a disulphide bond in the molecule used in the present invention, the addition amount when the thiazoline derivative or the isothiourea derivative is contained in the bleaching solution depends on the kind of the photographic material to be processed, the processing temperature, and the intended processing. 1 × 10 per treatment liquid, depending on time etc.
^-5 to 10 ^-1 mol is suitable, preferably 1 x 10 ^{-4 to} 5 x
It is 10 ^-2 mol.

In order to add the compound of the present invention to the treatment liquid, it is common to add it by dissolving it in water, an alkali organic acid organic solvent or the like in advance, but directly adding it to the bleaching bath as a powder, There is no effect on the bleaching promoting effect.

The bath having a bleaching ability of the present invention may contain an inorganic phosphoric acid having a chelating ability, an organic phosphonic acid, an aminopolyphosphonic acid, or a phosphonocarboxylic acid, in addition to the above-mentioned compounds, depending on the purpose. .

These compounds having a chelating ability can be used for the purpose of preventing the precipitation of iron salts, calcium and magnesium in a bath having a bleaching ability, preventing sulfuration, preventing the generation of bacteria and the like.

Further, for the purpose of preventing the generation of bacteria in a bath having a bleaching ability or a subsequent bath and imparting a fungicide-preventing ability to a sensitized material after processing, a thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole It is also possible to include a bactericidal agent such as the above and an antifungal agent.

The bath having the bleaching ability of the present invention may be one tank, or may be composed of two or more tanks. When it is composed of two or more tanks, it is preferable to adopt a multi-stage cascade system in which the rear tank is replenished and the overflow liquid generated thereby flows into the front tank.

In the case of using two or more tanks, the front tank may be a bleaching bath and the rear tank may be a bleach-fixing bath. In this case, the overflow solution of the bleaching bath can be made to flow into the bleach-fixing bath.

The present invention can be used in a bleaching bath and a bleach-fixing bath in the following steps.

1. Color development-bleach- (wash) -fixing-wash- (stable) 2. Color development-bleach-fix-wash- (stable) 3. Color development-bleach-bleach-fix-wash (stable) 4. Color development -Bleach-bleach-fix-fix-wash- (stable) 5. color development-bleach-fix-bleach-fix-wash- (stable) 6. black and white development-bleach- (reverse) -color develop-bleach-fix-
Washing with water- (Stable) In the above process, the process marked with () can be omitted depending on the type of sensitive material and the purpose of use.

The water washing step may be a conventional method that uses a relatively large amount of water or a water-saving method that reduces the amount of water.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-β
-Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, tetraphenylborate, p- (t-octyl) benzenesulfonate and the like. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

Examples of the aminophenol derivative include o-aminophenol, p-aminophenol, and 4-amino-2-.
Methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

LFA Meson's "Photographic Processing Chemistry", Focal Press (1966)
(LFAMason, “Photographic Processing Chemis
try ", Focal Press) 226-229, U.S. Pat. No. 2,193,01
Nos. 5, 2,592,364 and JP-A-48-64933 may be used. If desired, two or more color developing agents may be used in combination.

Color developers include pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Hydroxylamine, triethanolamine, compounds described in West German Patent Application (OLS) No. 2622950, preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary Development accelerators such as ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diols; dye-forming couplers; competing couplers; nucleating agents such as sodium boron hydride; 1-phenyl-3- Auxiliary developing agents such as pyrazolidone; tackifiers; ethylenediaminetetraacetic acid, nitrilotria Acids, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids represented by the compounds described in JP-A-58-195845, 1
-Hydroxyethylidene-1,1'-diphosphonic acid, organic phosphonic acids described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylenediamine-N, N, N ', N'- Aminophosphonic acids such as tetramethylenephosphonic acid, JP-A-52-102726
No. 53, No. 53-42730, No. 54-121127, No. 55-4024, No. 55
-4025, 55-126241, 55-65955, 55-65956
And Research Disclosure 18170 (1979
(May, 2010) described above and a chelating agent such as phosphonocarboxylic acid can be contained.

Color developing agent is generally about 0.1 g per color developing solution.
To about 30 g, more preferably about 1 g to about 15 g per color developer. Also, the pH of the color developer
Is usually greater than or equal to 7 and most commonly used from about 9 to about 13.

In the development processing of a reversal color light-sensitive material, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol. The developing agents can be used alone or in combination.

The bleaching step and fixing step after color development are as described above.

After the fixing step or the bleach-fixing step, it is common to carry out treatment steps such as washing and stabilizing, and only washing is performed, or conversely, only stabilizing treatment is provided without a substantial washing step. The simple treatment method of can also be used.

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 mold (for example, Journal of Antibacterial and Anfuyungal Ages (J.Antibact.Antifung.Agents) vol.11, No.5, p207-2
23 (1983) and compounds described in Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal"), metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or West Photograph・ Science and Engineering magazine (Phot.Sci.En
g.), Vol. 6, pp. 344-359 (1965), etc. may be added. It is particularly effective to add a chelating agent or a bactericide / antifungal agent.

The washing process is a multi-stage countercurrent washing with two or more tanks (for example, 2 to 9 tanks)
And you may save the wash water. JP-A-62-2 for washing water
Deionized water as described in 88838 is preferred. Further, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. In that case, various compounds are added to the stabilizing bath for the purpose of stabilizing the image.
For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monohydrate) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acids, dicarboxylic acids, polyalbonic acids and the like) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.),
Various additives such as bactericides (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used. Alternatively, two or more different kinds of target compounds may be used in combination. Further, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as a membrane pH adjuster after the treatment.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. The West German Patent No. 1 for saving silver in photosensitive materials.
The treatment using cobalt intensification or hydrogen peroxide intensification described in US Pat. No. 2,226,770 or US Pat. No. 3,674,499 may be applied.

Each processing time can be made shorter than the standard time within a range that does not cause any trouble in order to speed up processing.

In addition, in the case of continuous processing, a constant finish can be obtained by using a replenisher of each processing solution to prevent the composition of the solution from varying. 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, etc. may be provided in each treatment bath.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the silver halide color photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is 2 mol%
To 25 mol% of silver iodide.

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of 0.1 micron or less, large grains having a projected area diameter of up to 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse emulsion having a wide distribution.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographic Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press.
F. Duffin, Photographic Emulsion Chemistry (Focal Pr
ess, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikman et al, Mak).
ing and Coating Photographic Emulsion, Focal Pres
s, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. 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.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering.
eering) Vol. 6, pp. 159-165 (1962); Journal of Photo (Journal of Photo)
graphic Science), 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. Methods for making such emulsions are described in U.S. Pat. Nos. 3,574,628, 3,655,394 and British Patent 1,413,748. Also, JP-A-48-8600, 51-39027, 51-83097, 53-13
7133, 54-48521, 54-99419, 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

By using tabular grains in the silver halide photographic emulsion used in the present invention, improvement in sensitivity including improvement in color sensitizing efficiency by a sensitizing dye, improvement in relationship between sensitivity and graininess, improvement in sharpness, Improvement of development progress, improvement of covering power, improvement of crossover, etc. can be achieved.

Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, more than 8 or 5 or more and 8 or less.

The diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present technology, the tabular silver halide grains have a diameter of 0.3 to 5.0 μm, preferably 0.5 to 5.0 μm.
It is 3.0μ.

The thickness is 0.4 μm or less, preferably 0.3 μm or less, more preferably 0.2 μm or less.

Generally, tabular silver halide grains are tabular having two parallel planes, and thus the above-mentioned "thickness" is represented by the distance between two parallel planes constituting the tabular silver halide grain. It

The tabular silver halide grains can be used by monodispersing the grain size and / or thickness of the silver halide grains as described in JP-B-47-11386.

Here, the tabular silver halide grains being monodispersed means that 95% of the grains are dispersed within ± 60% of the number average grain size, preferably within ± 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

The proportion of tabular silver halide grains in the emulsion containing tabular silver halide grains used in the present technology is preferably 50% or more, and 70% or more with respect to the total projected area. Is more preferable, especially 90%
The above is preferable.

The tabular halogen composition is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride or silver iodochloride. Silver iodochloride is particularly preferred for use in the high-sensitivity light-sensitive material. In the case of silver iodochloride, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less.
It is not more than mol%. Further, silver chlorobromide and silver bromide are particularly preferable for the photosensitive material for printing.

The tabular grains may have a uniform halogen composition or two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the tabular silver iodobromide grains having a layered structure composed of a plurality of phases each having a different iodide content can be used. JP 58-1
13928 and JP-A-59-99433 disclose preferable examples of the halogen composition of tabular silver halide grains and the distribution of halogen within the grains. Generally, the desirable relationship between the relative iodide contents of the respective phases of the tabular silver halide grains is determined by the content of the development treatment (eg, a developing solution) applied to a light-sensitive material containing the tabular silver halide grains. It is desirable to select the optimum one according to the amount of the silver halide solvent contained therein) and the like.

The tabular silver halide grains are, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, a silver halide crystal which is epitaxially grown (for example, bromide). Crystals obtained by epitaxially growing silver chloride, silver iodobromide, silver iodide, etc. on silver, or hexagonal, octahedral silver iodide to silver chloride, silver bromide, silver iodide, chloroiodobromide. A crystal obtained by growing silver epitaxially) or the like may be used. Examples of these are U.S. Patent Nos. 4,435,501 and 4,463,0.
No. 87, etc.

Regarding the site for forming a latent image, it may be a particle in which the latent image is mainly formed on the surface of the particle, or a particle in which the latent image is mainly formed inside the particle. This can be selected depending on the use of the light-sensitive material using the tabular silver halide grains and the depth of the latent image inside the grain that can be developed by the developer for processing the light-sensitive material.

A preferred method of using the tabular silver halide grains of the present technology is Research Disclosure No. 22534 (1983
January, 2003), No. 25330 (May, 1985), which discloses the use based on the relationship between the thickness and optical properties of tabular grains, for example.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58
-248469 etc. are disclosed. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684, 4,142,900 and
4,459,353, British Patent 2,038,792, U.S. Patent 4,34
9,622, 4,395,478, 4,433,501, 4,463,087
No. 3,656,962, No. 3,852,067, JP-A-59-162540
No., etc.

Also, a mixture of particles having various crystal forms may be used.

Silver halide solvents are useful in promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add a halide salt, a silver salt or a deflocculant of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is taught in US Pat. Nos. 2,222,264, 2,448,534 and 3,320,069. Also U.S. Pat.
Conventional thioether ripening agents as described in 1,157, 3,574,628, and 3,737,313 can also be used. Alternatively, JP-A-53-82408 and JP-A-53-144319
It is also possible to use thione compounds such as those disclosed in US Pat.

The properties of the silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor, or they may be added along with one or more salts according to conventional methods. US Patent 2,44
No. 8,060, No. 2,628,167, No. 3,737,313, No. 3,772,031
And Research Disclosure, 134, 197
June 1993, as described in 13452, copper, iridium,
The presence of compounds such as lead, bismuth, cadmium, zinc, (chalcogen compounds such as sulfur, selenium and tellurium), gold and compounds of Group VII noble metals in the silver halide precipitation formation process You can control the characteristics. Japanese Patent Publication No. 58-1410, Moisa
r) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can undergo internal reduction sensitization of grains during the precipitation formation process.

Silver halide emulsions are usually chemically sensitized. Chemical sensitization is described by TH James, The Photographic Process, 4th Edition, published by Macmillan, 1977.
Year, (THJames, The Theory of the Photographic Pro
cess, 4th ed, Macmillan, 1977), using active gelatin as described on pages 67-76, and Research Disclosure, Volume 120, April 1974, 1200.
8; Research Disclosure, Volume 34, June 1975,
13452, U.S. Pat.Nos. 2,642,361, 3,297,446 and 3,7
72,031, 3,857,711, 3,901,714, 4,266,01
No. 8, and No. 3,904,415, and British Patent No. 1,315,75
PAg 5-10, pH 5-8 and temperature 30 as described in No. 5
It can be carried out with sulfur, selenium, chillyl, gold, platinum, palladium, iridium or combinations of these sensitizers at -80 ° C. Chemical sensitization is optimally carried out in the presence of sulfur-containing compounds such as gold compounds and thiocyanate compounds, rhodanine-based compounds and also US Pat. No. 3,857,711.
No. 4,266,018 and No. 4,054,457, or in the presence of a sulfur-containing compound such as a hypo, a thiourea compound, and a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azainpyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and Duffin, "Photoemulsion Chemistry", pages 138-143. ing. In addition to, or as an alternative to, chemical sensitization, U.S. Pat.
It can be reduction sensitized, for example with hydrogen, as described in US Pat.
Nos. 2,743,182 and 2,743,183 with reducing agents such as stannous chloride, thiourea dioxide, polyamines and / or low pAg (eg less than 5) and / or high pH (eg 8 It can be reduction-sensitized by the (larger) treatment. U.S. Pat.No. 3,917,48
Color sensitization can also be improved by the chemical sensitization method described in No. 5 and No. 3,966,476.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. The 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,
Thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, namely indolenine A nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a 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 have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
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 thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721) and an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,510). Described in), cadmium salt,
An azaindene compound or the like may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

Spectral sensitization of the emulsion of the present invention can be carried out at any stage of emulsion preparation.

Generally, a spectral sensitizing dye is added to a chemically sensitized emulsion before coating. U.S. Pat. No. 4,425,426 and the like disclose a method of adding to an emulsion before or during the start of chemical sensitization. In addition, a method of adding a spectral sensitizing dye to an emulsion before the formation of silver halide grains is completed is described in US Pat.
2,735,766, U.S. Patent 3,628,960, U.S. Patent 4,183,75
No. 6, and US Pat. No. 4,225,666.

Particularly in U.S. Pat.Nos. 4,183,756 and 4,225,666, a spectral sensitizing dye is added to an emulsion after the formation of stable nuclei for silver halide grain formation to increase photographic sensitivity and spectral sensitizing dye by silver halide grains. It is disclosed that there are advantages such as enhanced adsorption of

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound. , A urethane derivative, a urea derivative, an imidazole derivative, and 3-pyrazolidones. For example, U.S. Patents 2,400,532 and 2,4
23,549, 2,716,062, 3,617,280, 3,772,02
Those described in No. 1, No. 3,808,003 and British Patent No. 1,488,991 can be used.

In the silver halide photographic emulsion used in the present technology, for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance,
Various compounds can be included. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole. , Benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Etc ;: Mercaptopyrimidines; Mercaptotriazines; Thioketo compounds such as oxadrinethione; Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. be able to.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention include Research Disclosure (RD) 17643 (1978, 1
(Feb.) Section VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent coupler in which a coupling-active group is substituted with a coupling-off group is more preferable than a four-equivalent coupler in which the coupling active position is a hydrogen atom, because the coated silver amount can be reduced. Further, couplers in which the color-forming dye has an appropriate diffusibility, uncolored couplers, or DIR couplers that release a development inhibitor with a coupling reaction or couplers that release 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 are used.
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 of the color forming dye, especially the light fastness, while the α-benzoyl acetanilide type coupler can obtain a high coloring 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 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 particularly 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.
1,432 pyrazolobenzimidazoles, preferably pyrazolo [5,1] described in U.S. Pat.No. 3,725,067
-C] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and JP-A-60-33552
And the research discloser 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned.
The imidazo [1,2-b] described in U.S. Pat. No. 4,500,630 in terms of low yellow sub-absorption of a coloring dye and light fastness.
Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 1
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365 and 2,5-diacylamino-substituted phenol couplers and U.S. Pat.No. 3,446,622.
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like. Japanese Patent Application Nos. 59-93605 and 59-264277
Also, the cyan couplers described in JP-A 59-268135, in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc., are excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength region which the dyes formed from the magenta and cyan couplers have, it is preferable to use a colored coupler in combination with the color negative photosensitive material for photographing. Yellow colored magenta couplers described in U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 57-39413 or U.S. Pat.Nos. 4,004,929, 4,138,258 and British Patent No.
Typical examples include magenta colored cyan couplers described in 1,146,368 and the like.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such blur couplers are described in U.S. Pat.No. 4,366,237 and British Patent 2,125,570.
No. 96,5 for a specific example of a magenta coupler.
No. 70 and West German Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

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 the polymerized magenta coupler include British Patent No. 2,102,173, U.S. Patent No. 4,367,282, Japanese Patent Application No. 60-75041, and No. 60-11.
It is described in 3596.

Various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the photosensitive layer in order to satisfy the properties required for the light-sensitive material, or two or more layers in which the same compound is different. Can also be introduced.

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 present invention may include a coupler which releases a development inhibitor upon development, a so-called DIR coupler.

As the DIR coupler, for example, those releasing a heterocyclic mercapto type development inhibitor described in U.S. Pat. No. 3,227,554; those releasing a benzotriazole derivative described in JP-B-58-9942 as a development inhibitor; Kosho 51-16141
So-called colorless DIR couplers described in JP-A-52-90.
Release of nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after removal as described in US Pat. No. 4,24.
Release of a development inhibitor with an intramolecular nucleophilic reaction after elimination as described in JP-A-8,962 and JP-A-57-56837;
56-114946, 57-154234, 57-188035, 58-98
728, 58-209736, 58-209737, 58-209738
Nos. 58-209739 and 58-209740, which release a development inhibitor by electron transfer through a conjugated system after separation; described in JP-A-57-151944 and 58-217932. Which releases a diffusible development inhibitor whose development inhibiting ability is deactivated in the present solution: a film at the time of development by releasing the reactive compound described in Japanese Patent Application Nos. 59-38263 and 59-39653. Examples thereof include those that generate a development inhibitor by a medium reaction or deactivate the development inhibitor. Among the above-mentioned DIR couplers, more preferable ones in combination with the present invention are the developer inactivating type represented by JP-A-57-151944; US Pat. No. 4,248,962 and JP-A-57-154234. A typical timing type; a reaction type represented by Japanese Patent Application No. 59-39653, and among them, particularly preferable one is JP-A-57-1
No. 51944, No. 58-217932, Japanese Patent Application No. 59-75474, No. 59-822
Nos. 14, 59-82214, 59-90438 and the like, and DIR couplers described in JP-A-59-39653 and the like.

In the light-sensitive material of the present invention, a compound capable of releasing a nucleating agent or a development accelerator or a precursor thereof (hereinafter referred to as "development accelerator") in an image during development can be used. Typical examples of such compounds are given in British Patent 2,097,
No. 140 and No. 2,131,188, a coupler that releases a development inhibitor or the like by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, that is, DAR.
It is a coupler.

The development accelerator or the like released from the DAR coupler preferably has an adsorption group for silver halide, and specific examples of such a DAR coupler are disclosed in JP-A-59-157638 and JP-A-59-170840. No. DAR couplers which generate N-acyl-substituted hydrazines having a monocyclic or condensed-ring heterocycle as an adsorptive group, which leaves from the coupling active position of a photographic coupler at a sulfur atom or a nitrogen atom are particularly preferable. Specific examples are described in Japanese Patent Application No. 58-237101.

A compound having a development accelerator moiety in a coupler residue
Japanese Patent Application No. Sho 58-58, which releases a development accelerator by a redox reaction with the compound described in 60-37556 or a developing agent.
The compounds described in -214808 can also be used in the light-sensitive material of the present invention.

The DAR coupler is preferably incorporated in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention.
As described in JP-A-72640 or Japanese Patent Application No. 58-237104, it is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

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

A known anti-fading agent can be used in the light-sensitive material of the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, and methylenediene. Oxybenzenes,
Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, U.S. Pat.
553,794, 4,236,013, JP-B-51-6540, and benzotriazoles substituted with an aryl group described in EP 57,160, butadiene described in U.S. Pat.Nos. 4,450,229 and 4,195,999. Kinds, cinnamic acid esters described in U.S. Patent Nos. 3,705,805 and 3,707,375, benzophenones described in U.S. Patent No. 3,215,530 and British Patent No. 1,321,355,
Polymer compounds having an ultraviolet absorbing residue as described in US Pat. Nos. 3,761,272 and 4,431,726 can be used. U.S. Pat.Nos. 3,499,762 and 3,70
The UV-absorbing fluorescent whitening agents described in 0,455 may be used. Typical examples of the ultraviolet absorber are described in RD24239 (June 1984) and the like.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

The light-sensitive material produced by using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as irradiation or anti-halation prevention. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes,
Merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the light-sensitive material of the present invention, as a method for introducing a lipophilic compound such as a photographic coupler into the hydrophilic organic colloid layer,
Various methods such as oil-in-water dispersion method, latex dispersion method, solid dispersion method, and alkali dispersion method can be used, and a preferable method can be appropriately selected depending on the chemical structure and physicochemical properties of the compound to be introduced. it can.

(Example) Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 On a subbed cellulose triacetate film support,
A multi-layer color light-sensitive material A having the following composition was prepared.

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

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 4 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high sensitivity) Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 1: 1 internal high A)
gI type, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 5.0) Coating silver amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Odor Silver halide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface height A
gI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM-9 0.07 ExM-10 0.02 ExY-11 0.03 Solv- 1 0.3 Solv-4 0.05 7th layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 3, internal high A)
gI type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount 0.8 Gelatin 0.5 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv -1 0.02 9th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 2: 1, internal high A)
gI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Silver coating amount 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) A
gI type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Coating silver amount 0.20 Gelatin 0.5 ExS-3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.10 11th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 0.5 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, Equivalent diameter
0.07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles Diameter 1.5μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 In addition to the above components in each layer, emulsion stabilizer Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate The multi-layer color photographic light-sensitive material produced in this way has a color temperature of 48
After exposure of 20 CMS at 00 ° K, processing was performed by an automatic processor as follows. Since the bleaching solution shows the effect of the present invention on the processing performance, the aminopolycarboxylic acid secondary
The treatment was carried out using iron complex salts (compounds A and B) and those with various changes in pH.

In the above process, the stabilizing process was a three-stage countercurrent system in which the liquid flows in the order of →→.

The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5 g Water was added to 1.0 l pH 10.0 Bleaching liquid Compound A (Compound shown in Table-2) Amount shown in Table-2 Bleaching accelerator (Compound shown in Table-2) 7 × 10 ^-3 mol Compound B (Compound shown in Table-2 Amount shown in Table-2 Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g pH Value shown in Table-2 Water added 1.0 l Fixer Ethylenediaminetetraacetic acid disodium salt 5.0 g Sodium sulfite 4.0 Ammonium thiosulfate aqueous solution (70% W / V) 240 ml Sodium bisulfite 4.6 g Water was added 1.0 g pH 6.6 Stabilizer formalin (40%) 1.0 ml Poly Oxyethylene-p-monononylphenyl ether (average degree of polymerization: about 10) 0.3g 5-chloro-2-methyl-4-isothiazolin-3-one 0.03g Water added 1.0g In the bleach tank, Agitation No. 62-183460, the jet-stirring method and the circulation stirring method were applied to the bleach-fixing solution of Example 1. The former is the method constituting the present invention and the latter is the comparative example. The jet collision was set to occur 10 seconds after the photosensitive material entered the bleaching solution.

The amount of residual silver in the maximum density part, the yellow density in the minimum density part, and the maximum density of the cyan dye were measured for the samples treated as described above, and the results are shown in Table 2. The amount of residual silver was measured by a fluorescent X-ray method, and the other concentrations were measured by an X-ray 310 photographic densitometer.

<Compound used in Examples> (1) 1,2-Diaminopropanetetraacetic acid ferric complex salt (2) 1,3-Diaminopropanetetraacetic acid ferric complex salt (3) 1,4-Diaminobutanetetraacetic acid ferric salt 2 Iron complex salt (4) 1,5-diaminopentanetetraacetic acid ferric complex salt (5) Glycol ether diamine tetraacetic acid ferric iron complex salt (6) Iminodiacetic acid ferric iron complex salt (7) N-methyliminodiacetic acid ferric salt 2 Iron complex salt <Comparative compound> (1) Ethylenediaminetetraacetic acid ferric iron complex salt <Agitation> J: Jet type agitation described in JP-A-62-183460, Example-1 N: JP-A-62-183460, Example-1 Ordinary Circulating Agitation Described The results of Table-2 are described below.

Comparative compounds as seen in Nos. 1 and 2 (Comparative Examples)
In (1), the maximum cyan density at a pH of 5.0 is lowered, and a large color recoloring defect occurs. Also No. 3 and 4 (comparative example)
Then, the ferric iron complex salt which belongs to the present invention was used, but since the stirring method is outside the present invention, the minimum yellow density increases,
Occurrence of remarkable bleaching fog was observed, and defective color restoration of the cyan dye also occurred. In Nos. 5 and 6 (comparative examples), the pH was 6, and bleaching fog was remarkable even when jet collision was given. On the other hand, in No. 8 to 10, 12, and 13 of the present invention, bleaching is good and bleaching fog and color restoration failure are extremely small.

In particular, bleaching progresses significantly by using a bleaching accelerator,
It is also clear that the bleaching fog is further reduced by using the comparative compound- (1) together. The residual silver amount is 3μ
If it is less than g / cm ² , there is no problem in practical use, but less than 1.5 ug / cm ² is a particularly preferable region for finishing the photograph.

Example 2 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material was produced by coating each layer having the following composition in multiple layers.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

1st layer: antihalation layer Black colloidal silver 0.18 gelatin 0.40 2nd layer: intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U- 2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size of 0.
6μ, coefficient of variation for particle size 0.15) Silver 0.55 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 Sensitizing dye IV 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 4th layer (2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% silver iodide, average grain size of 0.
7μ, average aspect ratio 5.5, average thickness 0.2μ) Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 Sensitizing dye IV 3.0 × 10 ^-5 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30 Fifth layer (third red emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1μ) Sensitizing dye IX 5.4 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.4 × 10 ⁻⁴ Sensitizing dye IV 3.1 × 10 ⁻⁵ EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th Layer (intermediate layer) EX-5 0.040 HBS-1 0.020 EX-12 0.004 Gelatin 0.80 7th layer (1st green sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.
6μ, average aspect ratio 6.0, average thickness 0.15) Silver 0.40 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX- 7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75 Eighth layer (second green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (9 mol% silver iodide, average grain size of 0.
7μ, coefficient of variation for particle size 0.18) Silver 0.80 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.180 EX-8 0.010 EX-1 0.008 EX-7 0.012 HBS-1 0.160 HBS-4 0.008 Gelatin 1.10 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (12 mol% silver iodide, average grain size 1.0μ)
Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74 10th layer (yellow filter layer) Yellow colloidal silver 0.05 EX-5 0.08 HBS-3 0.03 Gelatin 0.95 11th layer (1st blue sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% silver iodide, Average particle size 0.
6μ, average aspect ratio 5.7, average thickness 0.15) Silver 0.24 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer) Monodisperse iodine Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.
8μ, variation coefficient for grain size 0.16) Silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.20 EX-10 0.015 HBS-1 0.03 Gelatin 0.46 13th layer (3rd blue emulsion layer) Silver iodobromide emulsion (Silver iodide 14 mol%, average particle size 1.3μ)
Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (1st protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average particle size 0.07μ)
Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72 Above for each layer In addition to the above ingredients, a gelatin hardening agent H-1 and a surfactant were added.

U-1; same as UV-1 of Example 1 U-2; same as UV-2 of Example 1 U-3; same as UV-3 of Example 1 U-4; UV-4 of Example 1 Same as U-5; same as UV-5 in Example 1 EX-1; same as ExC-9 in Example 1 EX-2; same as ExC-2 in Example 1 EX-3; ExC in Example 1 -4 same as EX-4; same as ExC-7 in Example 1 EX-5; same as Cpd-1 in Example 1 EX-6; same as ExC-8 in Example 1 but with an average molecular weight of 30,000 EX- 7; same as ExM-12 in Example 1 EX-8; same as ExY-13 in Example 1 EX-9; same as ExY-15 in Example 1 EX-10; same as ExC-16 in Example 1 .

EX-11; same as ExC-9 of Example 1, but R = H S-1; same as Cpd-5 of Example 1 S-2; same as Cpd-6 of Example 1 HBS-1; tricresyl phosphate HBS-2; dibutyl phthalate HBS-3; bis (2-ethylexyl) ) Phthalate HBS-4; same as Solv-4 of Example 1 H-1; same as H-1 of Example 1 The multi-layer color photographic light-sensitive material produced in this way has a color temperature of 48
After exposure of 10 CMS at 00 ° K, processing was performed by an automatic processor as follows. Since the bleaching solution shows the effect of the present invention on the processing performance, the aminopolycarboxylic acid secondary
The treatment was carried out using iron complex salts (compounds A and B) and those with various changes in pH.

In the above process, the stabilizing process was a three-stage countercurrent system in which the liquid flows in the order of →→.

The treatment liquid used was the same as in Example-1, and the stirring in the bleaching solution was also as described in Example-1. However,
In order to clarify the effect of the time until the jet collision occurs after the light-sensitive material enters the bleaching solution, one of the first discharge ports of the bleaching solution was adjusted and this time was variously changed.

The residual silver amount, minimum yellow density and maximum cyan density of the sample treated as described above were measured in the same manner as in Example-1, and the results are shown in Table-4.

As shown in Nos. 4 to 7 of Table 4, when the time until the jet collision is applied after introducing the light-sensitive material into the bleaching solution is 20 seconds, the residual silver amount is large and the minimum yellow density increases ( Bleaching fog) and a decrease in maximum cyan density (defective color restoration) are remarkable, but a remarkable improvement effect is observed when the time is within 15 seconds.

Example-3 The procedure of Example-2 was repeated except that the photosensitive materials used were changed to those described below.
Similar to the results of 2 and Table 4, the present invention showed extremely high effects in silver bleaching performance, prevention of bleaching fog, and prevention of cyan dye recoloring failure.

It has also been clarified that the processing method of the present invention can prevent deterioration of image storability which is a problem in rapid processing. The main results regarding this are shown in Table 7.

The image storability was evaluated by storing it for 2 weeks under the conditions of 60 ° C. and 70% relative humidity, and showing the change in the minimum density of magenta before and after.

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

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ^{2 of} silver for silver halide, colloidal silver and couplers, and for sensitizing dyes, it is mol per mol of silver halide in the same layer. It is shown by the number.

1st layer: Antihalation layer Black colloidal silver Silver coating amount 0.2 Gelatin 2.2 UV-1 0.1 UV-2 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 2nd layer: Intermediate layer Fine grain silver bromide (Equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.0 Cpd-2 0.2 Third layer: First red emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter)
0.7μ, coefficient of variation of equivalent spherical diameter 14%, tetradecahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, coefficient of variation of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-4 ExS-3 0.4 × 10 ^-4 ExS-4 0.3 × 10 ^-4 ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 4th layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, equivalent spherical diameter 1.
0Myu, sphere variation coefficient of 25% equivalent diameter, the plate-like particles, diameter / thickness ratio 4.0) silver coverage 0.55 Gelatin ^{0.7 ExS-1 3 × 10 -4} ExS-2 1 × 10 -4 ExS-3 0.3 × 10 - ⁴ ExS-4 0.3 × 10 ^-4 ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 Fifth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter) 1.2μ, variation coefficient of sphere equivalent diameter 28%, plate-like particles, diameter /
Thickness ratio 6.0) Silver coating amount 0.9 Gelatin 0.6 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Seventh layer: First green emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter 0.7 μ, variation coefficient of equivalent spherical diameter 14%, 14-sided grains) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, variation coefficient of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 8th layer: second green emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 1.0 μ, variation coefficient of equivalent spherical diameter 25%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 9th layer: Intermediate layer Gelatin 0.5 10th layer: 3rd green emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, high internal AgI type, equivalent spherical diameter)
1.2μ, variation coefficient of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.0 Gelatin 0.8 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Solv-1 0.2 11th layer: Yellow filter layer Cpd-3 0.05 Gelatin 0.5 Solv-1 0.1 12th layer: Intermediate layer Gelatin 0.5 Cpd-2 0.1 13th layer : 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 14%, tetradecahedral grain) Silver coating amount 0.1 Silver iodobromide Emulsion (AgI 4.0 mol%, internal high iodine type, sphere equivalent diameter 0.4μ, coefficient of variation of sphere equivalent diameter 22%, tetrahedral grain) Silver coating amount 0.05 Gelatin 1.0 ExS-8 3 × 10 ^-4 ExY-1 0.53 ExY -2 0.02 Solv-1 0.15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0 µ, variation coefficient of equivalent sphere diameter 16%, tetrahedron Particles) Silver coverage 0.19 gelatin ^{0.3 ExS-8 2 × 10 -4} ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer fine silver iodobromide (AgI2 mol%, uniform type, sphere-corresponding diameter 0.13
μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, spherical equivalent diameter 1.5 μ, variation coefficient of spherical equivalent diameter 28%, plate Particles, diameter /
Thickness ratio 5.0) Silver coating amount 1.0 Gelatin 0.5 ExS-8 1.5 × 10 ^-4 ExY-1 0.2 Solv 0.07 17th layer: 1st protective layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 Eighteenth layer: Second protective layer Fine silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 W-1 0.02 H-1 0.4 Cpd-5 1.0 As described above, the present invention also shows the effect of improving the image storability.

Example-4 The treatment process of Example-2 was changed as follows, and the others were performed in the same manner.

In the above treatment step, the washing with water was a countercurrent method from to. The overflow of the bleaching solution was introduced into the bleach-fixing solution. Next, the composition of each processing liquid will be described.

The composition of the treatment liquid used in the above steps is as follows.

<< Color Developer >> Same as in Example-1 << Bleaching Solution >> Compound A (Compounds listed in Table-6) Amount listed in Table-6 Compound B (Compound listed in Table-6) Listed in Table-6 Quantity Ethylenediaminetetraacetic acid 2 10.0 g Sodium salt Ammonium nitrate 10.0 g Ammonium bromide Bleach accelerator (compounds listed in Table 6) 5 × 10 ^-3 mol Water was added to 1.0 l << Bleaching fixer >> Compound A (Table-6 Compound described in Table 6 Amount described in Table 6 Compound B (Compound described in Table 6) Amount described in Table 6 Ethylenediaminetetraacetic acid 2 5.0 g Sodium salt 12.0 g Ammonium thiosulfate aqueous solution 240 ml (70%) Ammonia water was added, pH 7.3 was added, and 1.0 l << Washing liquid >> 20 mg / l of sodium chlorinated isocyanurate was added to deionized water having a conductivity of 5 μs / cm.

pH6.7 《Stabilizer》 Formalin (37% w / v) 2.0ml Polyoxyethylene-p-mono 0.3g Nonylphenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid 2, 0.06g Sodium salt water added 1.0 l As shown in Table 6, the present invention also showed good results in the step of bleaching after bleaching.

Example-5 When the processing methods No. 8 to No. 23 of the present invention described in Example-1 were carried out using the following color negative film, the same good effects as in Example-1 could be obtained. It was

Fuji Photo Film Co., Ltd. Fuji Color Super HR100 (Emulsion No. 6266689) Super Super HR200 (〃 523009) Super Super HR400 (〃 315059) Super Super HR1600 (〃 723005) Konica Color G × 100 (Emulsion No. 106) ) Same G × 400 (〃 861) Same G × 3200 (〃 751) Eastman Kodak Company Kodacolor VRG100 (Emulsion number 5095 104) Same VRG200 (〃 5096 123) Same VRG400 (〃 5097 123) Same VRG1000 (〃 5090 254 Example-6 The silver halide color photographic light-sensitive material (color negative film) described in Example-1 of the following patent was used in Example-1 of the present invention.
No. 8 ~ No. 22 of the treatment method was used to find the same effect as described in Example 1 of the following patent,
It was also confirmed that the treatment method of the present invention similarly exhibits excellent effects.

JP-A-57-151994 JP-A-57-94752 EP-A-161626A JP-A-60-143331 JP-A-60-185950 JP-A-60-138548

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-48-95834 (JP, A) JP-A-62-222252 (JP, A) JP-A-62-183460 (JP, A)

Claims (1)

[Claims] 1. An exposed silver halide color photographic light-sensitive material is subjected to color development processing, and then a pH of 5. containing at least one selected from the ferric complex salts of the following (1) to (7).
A method for processing a silver halide color photographic light-sensitive material, which comprises introducing into a bleaching solution of 0 to 4.0, and within 15 seconds thereafter, making a jet flow of the bleaching solution collide with the emulsion surface of the light-sensitive material. (1) 1,2-Diaminopropanetetraacetic acid ferric iron complex salt (2) 1,3-Diaminopropanetetraacetic acid ferric iron complex salt (3) 1,4-Diaminobutanetetraacetic acid ferric iron complex salt (4) 1, 5-Diaminopentanetetraacetic acid ferric iron complex salt (5) Glycol ether diaminetetraacetic acid ferric iron complex salt (6) Iminodiacetic acid ferric iron complex salt (7) N-Methyliminodiacetic acid ferric iron complex salt