JPH07111564B2 - 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, also simply referred to as a color light-sensitive material). The present invention relates to a processing method capable of producing silver and preventing bleaching fog, and can be suitably used for a high-sensitivity color light-sensitive material having a large amount of silver.

[Conventional technology]

In the processing of silver halide color photographic light-sensitive materials, color development processing and desilvering processing are essential.

Generally, in color development processing, the silver halide exposed by the color developing agent is reduced to produce silver, and
The oxidized color developing agent reacts with the coupler to give a dye image. In the desilvering process, the metallic silver produced in the color developing process is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and desilvered by a fixing agent. Through this desilvering process, only the dye image remains on the color light-sensitive material.

In this desilvering process, there are a case where the bleaching process and the fixing process are carried out separately, and a case where the bleaching process and the fixing process are carried out simultaneously (referred to as a bleach-fixing process in the present specification).

Usually, in addition to the above-mentioned basic steps, various auxiliary steps such as maintaining the photographic and physical quality of the image or improving the storability of the image are included. For example, each treatment step in a hardening bath, a stopping bath, an image stabilizing bath, and a washing bath.

In the method of performing the bleach-fixing process described above, a fixing process of dissolving and removing the soluble silver salt is performed at the same time as the bleaching described above. As a silver halide fixing agent used here, a thiosulfate salt has been conventionally used. Thiocyanates, halogen salts, thioureas, thioglycols, thiol compounds and the like are known. Among them, in actual photographic processing, thiosulfate has been used in most cases in terms of stability and price of silver complex salt. Whichever is used, the silver salt remaining in the fixing process is dissolved and removed by a compound which reacts with a silver halide such as sodium thiosulfate as a fixing solution component to form a soluble complex salt. When thiosulfate is used as the fixer component, the thiosulfate itself is also unstable such as being oxidized by air oxidation, and silver complex salts and halogen ions accumulate as the color photographic light-sensitive material is fixed. At the same time, the amount of thiosulfate free component, which is a fixing agent, decreases. Along with this, the fixing efficiency gradually decreases, and finally a fatigue phenomenon appears and it cannot be used. In general, in order to activate the fatigue fixing solution, a system is adopted in which an appropriate amount of a new fixing solution (regenerator or replenisher) is replenished and the fatigue fixing solution is discharged as an overflow. However, even when the fixing solution is repeatedly used by the replenishing method as described above, the fixing performance gradually changes and the fixing speed is gradually increased even though the concentration of free thiosulfate ion is sufficiently high as the usage frequency increases. It gradually changes, and finally, fixing failure occurs. The cause is considered to be that the soluble component contained in the emulsion layer of the processed light-sensitive material is eluted into the fixing solution and the eluted component is accumulated. As a solution to this problem, a method of adding a fixing accelerator to improve the fixing power and a method of removing halogen ions, which are a fixing inhibitor, are being studied, but they cause fixing failure or are economically difficult. Do not fit.

In any case, it can be said that thiosulfate, which is frequently used as a fixing agent, has a strong possibility of environmental pollution and has a serious drawback in terms of pollution prevention and economical efficiency.

On the other hand, the thiocyanates and halogen salts known as fixing agents other than the above thiosulfates each have their own drawbacks, and it is necessary to coexist with the thiosulfates after all, and as described above, the recovery of silver is not possible. If a part of it is discarded as an overflow during repeated use while performing it, the biological oxygen demand (BOD) and chemical oxygen demand (COD) cannot be satisfied, and there is a risk of environmental pollution. Since thiosulfate is itself a reducing agent, the fixing agent is susceptible to oxidative decomposition even by air oxidation and the like, resulting in an extremely disadvantageous effect in repeated reusing. Furthermore, when the above-mentioned thiosulfate is made to coexist with a thiocyanate or a halogen salt as a fixing agent component of a bleach-fixing solution having a fixing ability and a bleaching ability, each thiosulfate is itself a reducing agent. Since sulfite, which is required as a salt preservative, is also a reducing agent, the redox potential of the bleach-fixing solution becomes largely base, and the oxidizing power of the coexisting oxidizing agent is impaired, resulting in repeated regeneration of the solution. It has the drawback of being difficult to use. Therefore, there has been a strong demand for development of a processing method for photographic materials using a thiosulfate-free fixing solution or a bleach-fixing solution.

Therefore, for example, JP-A-52-134433 discloses a technique of using a bleach-fixing agent containing a certain amount of iodine ions. However, this conventional technique also requires rapid processing, the problem of bleaching fog, and the generation of stains associated therewith,
There are still points to be resolved.

The demand for rapid processing is also demanded from the problem of the bleaching agent component in the bleach-fixing solution. In general, an aminopolycarboxylic acid iron (III) (ferric) complex salt is often used as a bleaching agent, but this has a problem that it takes a long time to process. That is, as the bleaching agent, red blood salt, dichromate, ferric chloride, persulfate and the like are generally known, but they have pollution problems, stain generation, bleaching power problems and the like. On the other hand, ferric aminopolycarboxylic acid complex salts (especially ferric ethylenediaminetetraacetic acid ferric acid complex salts) have few pollution problems, and there are no problems with storage as dangerous substances such as persulfate salts, and thus they are the most present. Widely used. However, it is difficult to say that the bleaching power of ferric aminopolycarboxylic acid complex salts is sufficient, and it is difficult to apply it to a high-sensitivity light-sensitive material having a particularly large amount of silver. That is, the use of this as a bleaching agent can achieve the desired purpose in the case of bleaching or bleach-fixing a low-sensitivity silver halide color light-sensitive material mainly composed of a silver chlorobromide emulsion. When processing a high-sensitivity color light-sensitive material mainly composed of silver chloroiodide or silver iodobromide emulsion and color-sensitized, especially a color reversal light-sensitive material for photography and a color negative light-sensitive material for photography using a high silver content emulsion Have problems in that desilvering failure occurs and that it takes a long time to bleach silver.

For example, when a color negative photographic material for photographing is bleached using a bleaching solution of ferric aminopolycarboxylic acid complex salt, at least 4 minutes or more of bleaching time is required,
Moreover, in order to maintain the bleaching power, complicated management such as pH control of the bleaching solution and aeration is required. Even if such a management is carried out, the bleaching defect may still sometimes occur.

Further, for desilvering, it is necessary to carry out a treatment with a fixing solution for at least 3 minutes after the bleaching treatment, and it is strongly desired to shorten the time required for such desilvering treatment which requires a long time.

On the other hand, the German Patent No. 1
There is known a bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and thiosulfate as described in Japanese Patent No. 866,605, but the thiosulfate has the above-mentioned problems. In addition, when a ferric salt of aminopolycarboxylic acid, which originally has a weak oxidizing power (bleaching power), is allowed to coexist with a thiosulfate having a reducing power, the bleaching power is remarkably weakened, and a high-sensitivity, high-silver amount color photographic material for photographing. Is extremely difficult to desilver and cannot be put to practical use. Needless to say, various attempts have been made in the past to improve the drawbacks of such a bleach-fixing solution, but none of these effects are sufficient and they cannot be said to be practically sufficient.

As an improved technique in which the stability of the processing liquid is remarkably increased and the bleach-fixing speed is increased, for example, there is a disclosure described in JP-A-52-134433 mentioned above, in which bromide and iodide are contained at a high concentration. Although a bleach-fix solution has been proposed, according to the knowledge of the present inventors, there is a problem in the color restoration of the cyan dye which is intended to be processed in a very short time even if this conventional technique is used, and the color restoration property is It turns out that it doesn't improve much. The problem of color restoration failure is a phenomenon in which a sion dye formed by color development is reduced to a leuco dye to make a part of the dye colorless, and it is known that the problem easily occurs in a bleach-fixing solution.

It is known that this drawback can be ameliorated by increasing the pH of the bleach-fixing solution as described in U.S. Pat.No. 3,773,510, etc. However, increasing the pH, on the contrary, results in further weakening the silver bleaching power. Becomes

It was also found that the processing step of directly bleach-fixing a color developing solution using an iodine-containing bleach-fixing solution is accompanied by a serious failure of generating stain called bleaching fog.

Further, as another method for improving the color restoration failure, U.S. Pat.No. 3,189,452 discloses a method in which after bleach-fixing, a leuco dye is oxidized to a cyan dye by a red blood salt bleaching solution. The use of red blood salt has the above-mentioned problems such as pollution and is difficult to put into practical use.

As a method for solving these drawbacks, rapid bleaching and desilvering processing can be performed by treating with a bleaching solution containing ferric aminopolycarboxylic acid complex salt and then with a bleach-fixing solution containing ferric aminopolycarboxylic acid. JP-A-60-244949 and JP-A-61-75353 also disclose the proposal. However, with these processing methods, if the actual running processing is continued, the first complex salt accumulated in the bleach-fixing solution tends to cause defective color restoration even when using these cyan couplers, which are said to be difficult to leucoform, and particularly for a short time. In the case of the rapid processing, the leuco conversion of the cyan dye becomes large, and the color restoration failure becomes a serious obstacle.

Furthermore, if the concentration of ferric aminopolycarboxylic acid salt is raised or the pH is raised in order to minimize color restoration defects, stains called so-called bleaching fog are generated, which makes it impossible to satisfy for a long time. found.

Therefore, it is required to provide a desilvering method that can process a color photographic light-sensitive material having high sensitivity and high silver content for a long period of time without any problem.

[Object of the Invention]

A first object of the present invention is to provide an improved method for processing a color photographic light-sensitive material which does not deteriorate the photographic property even if it is processed for a short time. It is an object of the present invention to provide a processing method which does not cause color restoration failure even when processed and does not cause bleaching fog. A second object is to provide a processing method in which the performance is not deteriorated even if the processing solution is continuously processed for a long period of time, and deterioration (oxidative decomposition) of the bleach-fixing solution with time does not easily occur.

[Structure of Invention]

The above-mentioned object of the present invention is to provide a processing method in which an exposed silver halide color photographic material is subjected to bleach-fix processing after color development, wherein the silver halide photographic material is represented by the general formula [I] or the general formula [II]. It was achieved by a process for processing a color photographic light-sensitive material which contains at least one of the cyan dye-forming couplers shown and the bleach-fixing solution contains at least 1 mol of iodine ion per one.

General formula [I] General formula (II) (Wherein R ¹ , R ² and R ⁴ are substituted or unsubstituted aliphatic groups,
Represents an aryl group or a heterocyclic group, R ³ and R ⁶ are a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, an acylamino group, or R ³ and R ² together form a nitrogen-containing 5- or 6-membered ring Represents a non-metal atom group, R ⁵ represents an alkyl group having 2 or more carbon atoms which may have a substituent, or a methyl group having a substituent having 1 or more carbon atoms, R ⁷ represents hydrogen or 2 to 12 carbon atoms
In the formula ( ₁₎ , Z ₁ and R ₂ each represent a hydrogen atom or a group capable of splitting off during an oxidative coupling reaction with a developing agent, and n represents 0 or 1. The above groups include those having a substituent).

By using the processing method of the present invention, the above-mentioned object can be achieved.

That is, the inventors of the present invention have made extensive studies as to the development of a bleach-fixing solution which can be processed in an extremely short time, and as a result, in the method for processing a coupler photographic light-sensitive material using the cyan coupler of the present invention, iodine ions are fixed. When used as an agent, a bleach-fixing solution containing, for example, an iron (II) amiopolycarboate complex salt as an oxidant, has two major drawbacks: bleach fog and poor color restoration even when a high silver content photographic material is processed for a short time. The present invention has been accomplished by finding that the above can be solved.

The cyan dye comprising the cyan coupler according to the present invention is a type of dye which is extremely difficult to be a leuco dye, but the oxidation potential is too low in a bleach-fixing solution containing a large amount of thiosulfate and sulfite which are reducing agents. However, in a short-time treatment, a leuco dye is liable to be formed, which causes defective color restoration, whereas in the bleach-fixing solution using iodine ion as a fixing agent as in the present invention, a high silver content photographic light-sensitive material using a conventional coupler is used. In the case of a short time treatment, bleaching fog and color restoration failure are likely to occur, whereas in the case of the dye using the cyan coupler according to the present invention, bleaching fog is unlikely to occur and even a very short time treatment is required. This is a surprising feature in that color restoration failure hardly occurs when silver oxidation is completed.

Furthermore, even if the concentration of the oxidizing agent in the bleach-fixing solution is increased, or
It has been found that even if the pH is raised, an unexpected effect that stains called bleach fog hardly occur is brought about. This is because when a photographic light-sensitive material containing a cyan coupler which is a compound according to the present invention is used as a bleach-fixing solution using a conventional thiosulfate, the concentration of an oxidant is increased,
This was a surprising effect that could not have been predicted at all, considering that the problem of bleaching fog was always encountered when trying to achieve speedup by raising the pH.

Further, as a side effect, the bleach-fixing solution of the present invention is substantially free of sulfite ion and thiosulfate ion, which are easily deteriorated by air oxidation, so that it is not oxidized and is extremely safe for storage over time. Features were obtained.

This is an unexpected effect that is extremely convenient for rapid processing, based on the common knowledge that the storage stability of a processing solution is impaired by conventional high-temperature rapid processing. Furthermore, compared with thiosulfate ion, iodine ion has a zero COD load, and even if it is discharged, extremely favorable results can be obtained in terms of preventing pollution.

The present invention will be described in more detail below.

The bleach-fixing solution used in the present invention contains at least 1 mol of iodine ion per one.

As the iodide that forms iodide ions, for example, sodium iodide, lithium iodide, potassium iodide, ammonium iodide, iodoacetic acid and the like can be used.
The addition amount is arbitrary as long as the amount of iodine ion is 1 mol or more per 1 bleach-fixing solution, but preferably 1 mol to 8 mol per 1 is added. When it is less than 1 mol of iodine ion per one, the function as a fixing agent is insufficient. It may be added in excess of 8 moles, but a large effect cannot be obtained even if the amount added is further increased. The addition amount is more preferably 1.6 mol to 6 mol, and particularly preferably 2 mol to 5 mol.

In the present invention, iodine ions (such as the above iodides)
Other than that, it is not necessary to use a fixing agent, but other fixing agents may be used in combination. However, it is preferably substantially small amount, for example, thiosulfates such as sodium thiosulfate, ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiourea and thioether. Can be used together. Preferred fixing agents other than iodine ions are thiocyanate, thiourea, thioether and the like. The amount of these fixing agents is 1
It is preferably 0.001 mol to 0.5 mol, and more preferably 0.05 to 0.2 mol.

Next, the cyan dye-forming coupler represented by the general formula [I] or [II] of the present invention will be described.

In the general formulas [I] and [II], R ¹ , R ² and R ⁴ are fatty acid groups,
Preferably an aliphatic group having 1 to 32 carbon atoms (eg, methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), or heterocyclic group (eg, , 2-pyridyl group, 2-imidazole group, 2-furyl group, 6-quinolyl group, etc., and these are alkyl group, aryl group,
Heterocyclic group, alkoxy group (eg, methoxy group, 2-methoxyethoxy group, etc.), aryloxy group (eg, 2,
4-di-tert-amylphenoxy group, 2-chlorophenoxy group, α-cyanophenoxy group etc.), alkenyloxy group (eg 2-propenyloxy group etc.), acyl group (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, ethylcarbamoyl group, dimethylcarbamoyl group, Methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group, (eg, dipropylsulfamoylamino group, etc.), imide group (eg, succinimide group, hydantoinyl group, etc.), ureido group, (eg, phenylureido group) , Dimethylure Id group), an aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), an aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy It may be substituted with a group selected from a group, a nitro group, a sulfo group, a halogen atom and the like.

In the general formula [I], R ³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, an acylamino group or R ² and a non-metal atom group forming a nitrogen-containing 5- or 6-membered ring. Here, the substitutable substituent may be the substituent described for R ¹ .

In the general formula [I], n represents 0 or 1.

In the general formula [II], R ⁵ represents an optionally substituted alkyl group having 2 or more carbon atoms or a methyl group having a substituent having 1 or more carbon atoms. Preferable examples of the alkyl group having 2 or more carbon atoms include an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group and a cyclohexyl group, and a methyl group having a substituent group having 1 or more carbon atoms. Examples of the group include a cyclohexylmethyl group, a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group.

In the general formulas [I] and [II], R ⁶ represents a hydrogen atom, a halogen atom, an aliphatic group, an aryl group or an acylamino group.

In the general formula [II], R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 2 to 12 carbon atoms, preferably hydrogen,
It is an alkyl group having 5 or less carbon atoms. In the general formula [II], R ⁷ is preferably a hydrogen atom.

In the general formulas [I] and [II], Z ₁ and Z ₂ each represent a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) , An alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carbonylpropyloxy 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, heptaph Orobutyrylamino group, methanesulfonylamino group, toluenesulfonylamide group, etc.), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group) Etc.), an aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (eg,
Succinimide group, hydantoinyl group, etc.) and aromatic azo group (eg, phenylazo group, etc.). These leaving groups may include photographically useful groups.

In the general formula [I], preferred R ¹ is an aryl group or a heterocyclic group, a halogen atom, an alkyl group, an alkoxy group,
An aryl group substituted with 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, or a cyano group is more preferable.

In the general formula [I], when R ³ and R ² do not form a ring, R ²
Is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ³ is preferably a hydrogen atom.

In the general formula [II], R ⁴ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. General formula (II)
Preferred R ⁵ is an alkyl group having 2 to 15 carbon atoms,
And a methyl group having a substituent having 1 or more carbon atoms. In this case, the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group or an alkyloxy group.

In the general formula [II], R ⁵ 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 ⁶ in the general formula [II] is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

Preferred Z ₁ and Z _{2 in the} general formulas [I] and [II] are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group and a sulfonamide group, respectively.

In the general formula [II], Z ₂ is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

When n = 0 in the general formula [I], Z ₂ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

The cyan dye-forming coupler represented by the general formula [I] or [II] is usually used in a silver halide emulsion layer (particularly, a red-sensitive emulsion layer). The addition amount is 2 × 10 ^{-3 to} 5 × 10 ^-1
Mol / mol Ag, preferably 1 × 10 ^{-2 to} 5 × 10 ^-1 /, mol
Ag is used.

The method for synthesizing the cyan dye-forming couplers represented by the general formulas [I] and [II] is described in US Pat. Nos. 3,772,002 and 4,3.
No. 34,011, No. 4,327,173, No. 4,427,767 and the like can be easily synthesized based on the method described in the specification.

Specific compounds represented by the following general formulas [I] and [II] are listed, but the cyan coupler used in the present invention is not limited thereto.

The bleach-fixing solution used in the present invention may contain an aminopolycarboxylic acid iron [II] complex salt as a bleaching agent. This is a complex of III-valent iron (ferric) ion with aminopolycarboxylic acid or its salt.

As typical examples of these aminopolycarboxylic acids and salts thereof, A-1 ethylenediaminetetraacetic acid or its salts (salts of ammonium, sodium, potassium potassium, triethanolamine, etc.) A-2 trans-1,2-cyclohexanediamine Tetraacetic acid or its salt (〃) A-3 Dihydroxyethylglycinic acid or its salt (〃) A-4 1,3-diaminopropan-2-ol Tetraacetic acid or its salt (〃) A-5 1,3-diamino Propane tetraacetic acid or its salt (〃) A-6 1,2-diaminopropane tetraacetic acid or its salt (〃) A-7 Diethylenetriaminepentaacetic acid or its salt (〃) A-8 Ethylenediaminedioltohydroxyphenylacetic acid or its salt (〃) A-9 hydroxyethylethylenediaminetriacetic acid or its salt (〃) A-10 ethylene Amine dipropionate acid or a salt thereof (〃) A-11 ethylenediamine diacetic acid or a salt thereof (〃
) A-12 glycol ether diamine tetraacetic acid or its salt (〃) A-13 hydroxyethyliminodiacetic acid or its salt (〃) A-14 nitrilotriacetic acid or its salt (〃) A-15 nitrilotripropionic acid or its salt (〃
) A-16 triethylenetetramine hexaacetic acid or its salt (〃) A-17 ethylenediaminetetrapropionic acid or its salt (〃) etc. can be mentioned. It is not limited to these exemplified compounds.

In these compounds, especially A-1, A-2, A-5, A-
6, A-7 and A-12 are preferred.

The aminopolycarboxylic acid iron (III) complex salt may be used in the form of a complex salt, or an iron (III) salt such as ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, phosphoric acid An iron (III) ion complex salt may be formed in a solution using ferric iron or the like and aminopolycarboxylic acid or a salt thereof. When used in the form of complex salt, one kind of complex salt may be used, or two or more kinds of complex salt may be used. Meanwhile, the second
When a complex salt is formed in a solution using an iron salt and aminopolycarboxylic acid, one type or two or more types of ferric salts may be used. Furthermore, one or two aminopolycarboxylic acids can be used.
You may use more than one kind. Further, in any case, the aminopolycarboxylic acid may be used in excess to form the iron (III) ion complex salt. The aminopolycarboxylic acid and iron complex salt may be used as an ammonium salt, a sodium salt, a potassium salt, or a triethanolamine salt, and two or more kinds thereof may be used in combination.

Further, the bleach-fixing solution containing the iron (III) ion complex may contain a metal ion complex salt of cobalt, copper, nickel, zinc or the like other than iron.

The amount of the bleaching agent used in the present invention is preferably 0.1 to 3 mol, and more preferably 0.2 to 1.0 mol, per 1 bleach-fixing solution.

Further, the bleach-fixing solution used in the present invention includes compounds containing a mercapto group or a disulfide bond, such as those disclosed in JP-A Nos. 61-112146, 61-47961 and 61-252.
Bleach-fixing accelerators such as those listed in Nos. 552 and 61-22295 can be incorporated.

The bleach-fixing solution used in the present invention may contain various additives.

For example, in the bleach-fixing solution of the present invention, a compound having pyrrolidonic acid in its molecular structure can be preferably used.

Examples of the compound having a pyrrolidone nucleus in the molecular structure that can be used include a polymerizable polymer in which the main chain or side chain pyrrolidone nucleus substitutes at any position in any number, and is a homopolymer thereof. It may be a copolymer obtained by polymerizing two or more kinds of copolymerization components. In the latter case, a polymer as a copolymer component having a pyrrolidone nucleus unit in the molecular structure is copolymerized with another polymer having no pyrrolidone nucleus unit in the molecular structure to be copolymerized with the polymer as the copolymerization component. In the copolymer obtained at most,
Those containing 20% or more are preferable, and those containing 30% or more are particularly preferable.

Typical examples of compounds that can be used include the following.

[B-1] Poly-N-vinyl-2-pyrrolidone (* Note 1) [B-2] Poly-N- (2-acryloyloxy)
Ethyl-1-pyrrolidone [B-3] Poly-N-glycidyl-2-pyrrolidone [B-4] Poly-N-allyl-2-pyrrolidone [B-5] Poly-N, N-dimethyl-N [3 (1-pyrrolidonyl ) -2-Hydroxy] propyl-amine-
N'-acryloylimine [B-6] copoly-N-vinyl-2-pyrrolidone / N
-Acryloylmorpholink (molar ratio 42:58) [B-7] Copoly-N-vinyl-2-pyrrolidone / N
-Acryloylpiperidine (molar ratio 35:65) [B-8] poly-N-vinyl-2-pyrrolidone / N-
Methacryloyl-2-methylimidazole (molar ratio 55: 4
5) [B-9] copoly-N- (2-acryloyloxy) -ethyl-2-pyrrolidone / acrylic acid diethylamide (molar ratio 60:40) [B-10] copoly-N- (2-methacryloyloxy) ethyl 2-pyrrolidone / sodium acrylate (molar ratio 75:25) [B-11] copoly-N- (3-acryloyloxy)
Propyl-2-pyrrolidone / methacryloyl methylacetate (molar ratio 65:35) [B-12] copoly-N, N-dimethyl-N- [3- (γ
-Pyrrolidonyl) -2-hydroxy] propylamine-
N'-acryloylimine / ethyl acrylate (molar ratio
70:35) [B-13] Copoly-N-vinyl-3-pyrrolidone / vinyl acetate (molar ratio 70:30) [B-14] Copoly-N-vinyl-2-pyrrolidone / methyl acrylate (molar ratio 70 : 30) [B-15] copoly-N-vinyl-2-pyrrolidone / styrene (molar ratio 80:20) [B-16] copoly-N-vinyl-2-pyrrolidone / acrylic acid amide / N-vinyl-2 -Methylimidazole (molar ratio 50:30:20) [B-17] copoly-N-vinyl-2-pyrrolidone / N-
(1,1-Dimethyl-3-oxo) -butyl-acrylamide (molar ratio 70:30) [B-18] copoly-N-allyl-2-pyrrolidone / vinyl acetate (molar ratio 64:36) [B-19 ] Copoly-N-vinyl-2-pyrrolidone / 4-
Vinyl pyridine (molar ratio 60:40) [B-20] copoly-N-vinyl-2-pyrrolidone / ethyl acrylate / acrylic acid monoethanolamine acid (molar ratio 50: 45: 5) [B-21] copoly- N-vinyl-2-pyrrolidone / piperidinomaleamic acid piperidine acid (molar ratio 53:47) [B-22] copoly-N-vinylpyrrolidone / 4-vinylpyridino-N-methyliodide (molar ratio 42:58 ) [B-23] Copoly-N-vinylpyrrolidone / thiourea half ammonium salt of maleic acid (molar ratio 60:40) * The exemplified polymer [1] of Note 1 is General Aniline & Film Corp. (General aniline and film
corp.) under the trade name of PVP K-30.PVP K-60, PVP K-90.

As mentioned above, some of them are on the market and can be easily obtained, and John Willie & Somes
Published by Inco (John Wilery and Soms, Inc.) (1961)
It can be easily synthesized according to the method described in the Preparative Methods of Polymer Chemistry by WR Sorenson, TW Canpbell. .

When a polymer having a pyrrolidone nucleus is added to the bleach-fixing solution, it is generally preferably 5 to 200 g / l, and when silver ions are eluted and accumulated from the emulsion layer of the nucleus-processed photographic material in the processing bath, for example, silver. When the amount of ions accumulated is as large as 45 g / l, 30 to 80 g / l is sufficient. In addition, the treatment temperature in the bath may be taken into consideration, and the concentration may be arbitrarily determined without being limited to the above-mentioned range with reference to the type of polymer used and the iodine ion concentration as a coexisting fixing agent.

Other additives include, for example, ammonium nitrate,
Sodium nitrate such as sodium nitrate, sulfite such as sodium sulfite and ammonium sulfite, nitric acid, borax, sodium metaborate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, acetic acid, sodium acetate, phosphorous acid, A pH adjusting agent such as phosphoric acid, sodium phosphate, citric acid, tartaric acid or the like can be contained alone or in combination of two or more kinds. Further, various antifoaming agents or surfactants can be contained, and bromides such as potassium bromide and ammonium bromide, and further hydroxylamine and hydroxylamine derivatives, hydrazine, and bisulfite adducts of aldehyde compounds. You can also

The pH of the bleach-fixing solution according to the present invention is preferably 4.0 to 9.5, more preferably 5.0 to 9.5, and further preferably 5.5 to 8.2.

In the present invention, the bleach-fixing time is preferably 20 seconds to 4 minutes, more preferably 20 seconds to 2 minutes.

〔Example〕

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all of the following examples, the amount added in the silver halide color photographic light-sensitive material was per 1 m ² , and the silver halide and colloidal silver were converted to silver.

Example 1 The following layers were sequentially coated on a cellulose triacetate support to prepare a multilayer color photographic light-sensitive material sample.

1st layer: antihalation layer (HC layer) An antihalation layer consisting of 0.16 g / m ² of black colloidal silver and 1.4 g / m ² of gelatin.

Second layer: Undercoat layer (IG layer) An undercoat layer made of 1.9 g / m ² of gelatin.

Third layer: Red-sensitive silver halide emulsion layer (R layer) The silver halide used in this layer is as follows.

The silver halide used for this layer is as follows.

Monodisperse spherical particles of silver iodobromide with an average particle size of 0.5 μm containing 4.0 mol% of AgI and an average particle size of 1.0 mol% containing 6.0 mol% of Agl.
Obtained by adding 1 μm monodisperse spherical particles at a ratio of 1: 1 (coating amount 2.34 g / m ² in terms of silver amount).

Each of the above silver halide emulsion layers is red-sensitized, various exemplary cyan couplers shown in Table 1 below or comparative cyan couplers of 0.2 mol / mol Ag, and 0.006 mol / mol Ag of the following. Colored cyan coupler (CC-1) is dissolved in tricresyl phosphate (hereinafter referred to as TCP), and the inhibitor is dissolved in methanol, and the dispersion is emulsified and dispersed in an aqueous solution containing gelatin. Red-sensitive silver halide emulsion layer.

Fourth layer: middle layer (2G layer) 0.14 g / m ² of 2.5-di-t-butylhydroquinone and 0.07 g
An intermediate layer made of / m ² dibutyl phthalate (hereinafter referred to as DBP).

Fifth layer: green-sensitive silver halide emulsion layer (G layer) The silver halide used in this layer is as follows.

Monodispersed spherical grains of silver iodobromide containing 3.5 mol% of Agl and having an average particle size of 0.4 μm and tabular grains of silver iodobromide of the same composition and an aspect ratio of 8 were added at a ratio of 1: 2. What was obtained (coating amount was 1.9 g / m ² in terms of silver amount).

0.15 mol / mol of each of the above silver halide emulsions sensitized with green sensitivity and the following magenta coupler (M-1)
A green-sensitive silver halide emulsion layer containing a dispersion of Ag and TCP in which 0.015 mol / mol Ag of the following colored magenta coupler (CM-1) is dissolved in an aqueous solution containing gelatin.

Sixth layer: 0.3 g / m ² of yellow colloidal silver and 0.22 g of antifouling agent (2.5-di-t-octylhydroquinone) dissolved
Yellow filter layer containing 0.11 g / m ² DBP and 2.1 g / m ² gelatin.

Layer 7: Low-sensitivity blue-sensitive silver halide emulsion layer (layer B) The silver halide used in this layer is as follows.

Monodisperse spherical particles containing 4 mol% of Agl and having an average particle diameter of 0.5 μm (coating amount is 0.7 g / m ² in terms of silver amount).

Blue-sensitive sensitization of the above silver halide emulsion,
The following squid coupler (Y-1) of 29 mol / mol Ag is TC
A blue-sensitive silver halide emulsion layer which is dissolved in P and is emulsified and dispersed in an aqueous solution containing gelatin.

Eighth layer: High-sensitivity blue-sensitive silver halide emulsion (layer B) Same as the seventh layer. However, as the silver halide grains, monodispersed spherical grains containing 7 mol% of Agl and having an average grain size of 1.0 μm were used (the coating amount was 0.6 g / m ² in terms of silver amount).

Ninth layer: protective layer (3G layer) A protective layer containing 0.9 g / m ² of gelatin.

In addition to the above, each layer contains a gelatin hardening agent (1,2-bisvinylsulfonylethane and 2,4-dichloro-6-hydroxy-
s-triazine sodium salt) and a surfactant were contained.

The coated silver amount was 60 mg / 100 m ³ .

The couplers and the like used in each layer are as shown below.

Comparison coupler (1) Comparison coupler (2) Colored cyan coupler (CC-1) 1-hydroxy-4-4 [4- (hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4-di-t -Amylphenoxy) butyl] -2-naphthamide disodium salt Magenta coupler (M-1) 1- (2,4,6-trichlorophenyl) -3-{[α-
(2,4-Di-t-amylphenoxy-acetamido] benzamido} -3-virazolo) one Colored magenta coupler (CM-1) 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone yellow coupler (Y-1) α- [4- (benzyl-2-phenyl-3,5-dioxo-1,2 , 4-Triazolidinyl)]-α-pivaloyl-2
-Chloro-5- [γ- (2,4-di-t-amylphenoxy) butanamide] acetanilide Each sample was exposed (16 CMS) through a wedge,
A dye image was obtained by the following processing steps.

Processing process Color development 3 minutes 15 seconds (38 ° C) Bleach-fixing 3 minutes (38 ° C) 1st stabilizing solution 1 minute 20-33 ° C 2nd stabilizing solution 1 minute 20-30 ° C Drying Processing solution composition used in each processing step Is as follows.

(Color developer) N-ethyl-N-β-hydroxyethylaminoaniline sulfate 4.8 g Anhydrous potassium sulfite 2.0 g Hydroxylamine 1/2 sulfate 3.0 g Potassium carbonate 30 g Sodium bromide 1.3 g Sodium diethylenetriamine bentaacetate 2.0 g Add water to make 1 and adjust to pH = 10.0 with 50% KOH and H ₂ SO ₄ .

(Bleach-fixing solution) The portions using the composition shown in Table-1 were adjusted to the values shown in Table-1 by using acetic acid or aqueous ammonia (28%). Further, silver powder was added to reduce ferric aminoborcarboxylate to form ferrous rust salt. The amount of silver powder was FeII / (FeIII + Fe
II) was added while being prepared so as to be 0.2 to 0.25.

(First Stabilizing Solution) Isothiazolin-3-one 0.1 g Add water to make 1.

(2nd stabilizing solution) Formalin (3% aqueous solution) 1.5 Unidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 Add water to make 1 The sample obtained by the treatment was colored cyan with an optical densitometer. The maximum and minimum concentrations of the system were measured. The minimum density was based on the one subjected to a termination treatment with a 4% aqueous solution of acetic acid before the bleach-fixing treatment, and the difference was noted as bleach fog. Further, the amount of residual silver in the maximum density part was measured as a transmission density with an infrared densitometer (measurement wavelength: 1200 nm) and converted into the amount of silver in a conversion table.

Further, the sample after each concentration measurement was treated with an aqueous solution of red blood salt (K ₃ Fe (CN) ₆ ) 20 g / l at 30 ° C. for 5 minutes to develop all of the leuco dye, then washed with water and dried. Measure the cyan dye density of the maximum density part of this sample with an optical densitometer, divide the cyan dye maximum density value obtained earlier by this density, multiply by 100, and measure the color restoration,
The color reversion property is shown in Table 1.

The iron complex salts shown in the table are as follows.

EDTAFe (III) NH ₄ ...... Ethylenediaminetetraacetic acid iron (II
I) Ammonium salt EDTAFe (III) NH ₄ ...... Ethylenediamine iron pentaacetate (II
I) Ammonium salt M-EDTAFe (III) NH ₄ …… 1,2 Diaminopropane iron tetraacetate (III) Ammonium salt PDTAFe (III) NH ₄ …… 1,3 Diaminopropane tetraacetate iron (I
II) ammonium salt _{Cy-DTAFe (III) NH 4} ...... trans - cyclohex-one diamine tetraacetic acid iron (III) ammonium salt _{G-EDTAFe (III) NH 4} ...... glycolate - Rue - Terujiamin tetraacetic acid iron (III) ammonium salt As is clear from the results shown in Table 1, the bleach-fix solution containing 1.0 mol or more of iodine ions as a fixing agent has been used as a fixing agent in the past. (NH ₄ ) ₂ S ₂ O ₂ was used alone. There is some improvement in bleaching fog and desilvering property compared to the liquor (Samples N0.1-8 and 11 and Samples N0.9-10 and 12).
~ Comparison with 31).

However, it is clear from Table (1) that the combination with the light-sensitive material using the cyan coupler of the present invention markedly improves the bleaching fog, desilvering property and color-restoring property. (In Table 1, the case of applying the present invention is shown by enclosing it with a thick line). Note that the bleach-fixing agents of Sample 17 and later do not contain sulfite and the like, and exhibit fixing action only with iodide.

In addition, ferric iron complex salt was added to EDTAFe, DTPAFe, M-EDTAFe, PDTAFe, CyD
When TAFe or G-EDTAFe is used, almost the same effect is obtained. Among them, it can be seen that the use of DTPAFe and PDTAFe enhances the effect of improving the color reversion property and desilvering property. Further, the exemplified compounds C-37, C-38, C63, C'-4 and C'-9 were examined as cyan couplers instead of the cyan coupler used in Example (1).
The same effect as in the above example could be obtained.

[Effects of the Invention] According to the present invention as described above, the photographic property is not deteriorated even if the processing is performed for a short period of time, and even if the high-sensitivity and high-silver content photographic light-sensitive material is processed for a long period of time, no color restoration failure occurs. Further, it is possible to provide a processing method in which bleaching fog does not easily occur, performance does not deteriorate even when the processing solution is continuously processed for a long period of time, and deterioration (oxidative decomposition) of the solution over time does not easily occur.

Claims (1)

[Claims] 1. A processing method for subjecting an exposed silver halide color photographic light-sensitive material to a bleach-fixing treatment after color development, wherein the silver halide color photographic light-sensitive material is represented by the general formula [I] or the general formula [II]. A method for processing a silver halide color photographic light-sensitive material, which comprises at least one cyan dye-forming coupler and the bleach-fixing solution contains at least 1 mol of iodine ion per one. General formula [I] General formula (II) (In the formula, R ¹ , R ² and R ⁴ represent an aliphatic group, an aryl group or a heterocyclic group, and R ³ and R ⁶ represent a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, an acylamino group, or R ³ Represents a nonmetallic atom group forming a nitrogen-containing 5- or 6-membered ring with R ² , and R ⁵ has an alkyl group having 2 or more carbon atoms which may have a substituent or a substituent having 1 or more carbon atoms. Represents a methyl group, R ⁷ represents hydrogen or an alkyl group having 2 to 12 carbon atoms,
Z ₁ and Z ₂ represent a hydrogen atom or a group capable of splitting off upon oxidative coupling reaction with a developing agent, and n represents 0 or 1. The above groups include those having a substituent).