JP2571086B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and particularly to a method for processing a color developing solution in the processing of a silver halide color photographic light-sensitive material for photography. The present invention relates to an improved processing method in which processing performance does not fluctuate even when the replenishment amount is reduced.

(Prior Art) In recent years, from the necessity of preventing water pollution and reducing treatment costs, research on techniques for reducing the amount of waste liquid in treatment has been promoted, and practical use has been achieved in some treatment steps.
In particular, various methods have been conventionally proposed for the color development process, since the pollution load of the waste liquid is very large. For example, JP-A-54-37731, JP-A-56-1048, JP-A-56
No.-1049, No.56-27142, No.56-33644, No.56-1490
No. 36, including methods using electrodialysis described in JP-B-61-10199, JP-B-55-15171, activated carbon described in JP-A-58-14831, and JP-A-52-105820. Ion exchange membranes, JP-A-55-144240, JP-A-57-146249, JP-A-61-95
Various methods for regenerating a color developing solution using an ion exchange resin described in JP-A-352 can be mentioned.

However, all of the above methods require the analysis of the developer to control the composition, which requires advanced management techniques and expensive equipment, and as a result, is only performed in some large-scale laboratories. That is the fact.

On the other hand, a low replenishment processing method of reducing the replenishment amount by adjusting the composition of a replenisher of a color developer (hereinafter referred to as a color developer replenisher) without depending on the regeneration as described above is also performed. Adjustment of the replenisher composition in low replenishment processing means, for example, concentrating consumable components such as color developing agents and preservatives so that the required amount of components is supplied even if the replenishment amount is reduced. There. When a silver halide color photographic light-sensitive material is processed, halogen ions are released into a color developing solution.
In the low replenishment processing, in particular, the bromine ion concentration in the color developing solution increases, resulting in suppression of development. Therefore, in order to prevent this, measures such as reducing the bromide concentration in the replenisher in comparison with the normal replenishment treatment are generally performed.

Such a low replenishment process has the advantage that a large amount of light-sensitive material is processed every day, and when the amount of replenishment is small, the analysis of the composition of each solution is not required.

However, when the amount of the photosensitive material to be processed (hereinafter simply referred to as the processing amount) is small or when the amount of the replenishment amount is large, the residence time in the processing tank is increased by reducing the replenishment amount. In the meantime, there is a drawback that the evaporation of water and the oxidation of the preservative and the developing agent progress to change the composition of the developing solution, thereby significantly changing the processing performance. Although the amount of the replenisher of the color developing solution varies by connexion to the type of the photosensitive material, taking a photographic color negative film as an example, is usually 1 m ² per about 1200 ml, the problem noticeable when reduced to below 1 m ² per 700ml It is. Such a problem can be corrected to some extent if the processing amount is constant every day. However, it is usual in the art that there is a large fluctuation in the processing amount due to the difference in the day of the week, month, and season. Therefore, a large low replenishment process makes it extremely difficult to maintain a desired liquid composition, and particularly results in a remarkable fluctuation in the yellow tone and fog density of the processed light-sensitive material.

For this reason, the low replenishment process has an advantage in simplicity, but can be performed only under limited processing conditions,
In fact, it was not possible to drastically reduce the amount of replenishment.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to enable a large reduction in the amount of replenishment and a stable performance to be ensured even when a small amount of processing or a large change in the processing amount is involved. To provide a processing method. The second object is to spread the treatment to lower pollution widely. Further, a third object is to provide an inexpensive processing method in a wide range.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide emulsion layer containing a cyan coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide containing a yellow coupler on a support. Having the following general formula (I) having an emulsion layer and at least one of the yellow couplers having an equivalent molecular weight of 450 to 720:
A silver halide color photographic light-sensitive material which is a lipophilic 2-equivalent yellow coupler represented by the formula (I) and contains a high boiling point organic solvent in a weight ratio of 0.5 or less with respect to the total amount of the yellow coupler contained in the emulsion layer, A silver halide color photographic material (hereinafter, simply referred to as a color photographic material), characterized in that it is processed with a color developing solution that replenishes 200 ml or more and 500 ml or less per 1 m ^{2 of} silver color photographic material. Was achieved.

General formula [I] In the general formula [I], R ^I and R ^III are groups (including atoms) substitutable on a benzene ring, R ^II is a hydrogen atom, a halogen atom or an aliphatic oxy group, and m is 0 or 1 to 5 An integer, n is 0 or an integer of 1 to 4, and X is an aromatic first
And represents a group which can be removed by a coupling reaction with an oxidized secondary amine developing agent. However, when m is plural, (R ^I ) _m may be the same or different, and when n is plural, (R ^III ) _n may be the same or different. Also R ^I , R
^II , R ^III or X may be a divalent to tetravalent linking group to form a dimer or tetramer of a yellow coupler represented by the general formula [I].

The "equivalent molecular weight" of the yellow coupler referred to in the present invention is represented by the following formula, where N is the number of coupling positions in one molecule of the yellow coupler represented by the general formula [I], and M is the molecular weight of one molecule. It is defined.

The yellow coupler of the general formula (I) is a 2-equivalent coupler having an equivalent molecular weight of 450 to 720 as defined above, but preferably has an equivalent molecular weight of 500 to 720, more preferably 52 to 720.
0 to 710.

It is preferable that the yellow coupler represented by the general formula (I) does not contain a water-soluble group such as sulfonic acid and carboxylic acid.

The dye formed by coupling the yellow coupler represented by the general formula (I) with the oxidized aromatic primary amine developing agent is preferably non-diffusible,
D _B / D _A defined in 2-3 pp JP 50-155226 is preferably if 0.25 or less of the present invention.

Here, in order to form a yellow dye image, generally, α
A pivaloylacetanilide-based coupler and an α-benzoylacetanilide-based coupler are used. However, the present inventors have found that the performance of an α-pivaloylacetanilide-based coupler is extremely liable to fluctuate in the low replenishment treatment aimed at by the present invention. This phenomenon is
-It is presumed to be caused by poor coupling efficiency between the pivaloylacetanilide-based coupler and the color developing agent.

On the other hand, the α-benzoylacetanilide-based coupler was expected to be less susceptible to fluctuations in the processing solution composition in low replenishment processing due to the high coupling efficiency with the color developing agent, but no particular advantage was recognized. .

The present inventors have conducted intensive studies on this point, and as a result, by specifying the molecular weight of the α-benzoylacetanilide-based coupler represented by the general formula (I) and the amount of the high boiling point organic solvent to be used, the finish performance in the low replenishment treatment is reduced. It has been found that the fluctuation is remarkably suppressed, and the present invention has been achieved.

Although the mechanism of such an effect is unknown, the thickness and color developing property of the yellow emulsion layer by specifying the molecular weight and the high boiling point organic amount are in a state that is hardly susceptible to changes in conditions such as the processing solution composition in low replenishment processing. It is thought to be.

Next, each substituent in the yellow coupler represented by formula (I) used in the present invention will be described in detail.

Examples of R ^I and R ^III include a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aliphatic group having 1 to 20 carbon atoms. An oxy group, an aromatic oxy group having 6 to 20 carbon atoms, a carbonamide group having 2 to 24 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, and 0 carbon atoms
~ 24 carbamoyl group, C0-20 sulfamoyl group, C2-20 acyloxy group, C2-20 aliphatic oxycarbonyl group, C2-24 substituted amino group, C1 ~ 1 24 aliphatic thio groups, ureido group having 0 to 20 carbon atoms, sulfamoylamino group having 0 to 20 carbon atoms, cyano group, aliphatic oxycarbonylamino group having 2 to 20 carbon atoms, 4 to 20 carbon atoms Examples include an imide group, an aliphatic sulfonyl group having 1 to 20 carbon atoms, an aromatic sulfonyl group having 6 to 20 carbon atoms, and a heterocyclic group having 1 to 20 carbon atoms. R ^II is a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom) or an aliphatic oxy group having 1 to 24 carbon atoms. X is a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developing agent, and is specifically represented by the following general formulas [II], [III] and [IV].

Formula (II) -O-R ^IV general formula [III] -S-R ^V general formula [IV] In the general formula (II), R ^IV is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, an aliphatic sulfonyl group having 1 to 24 carbon atoms or a carbon atom. Number 6
To 24 aromatic sulfonyl groups.

In the general formula [III], R ^V represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 28 carbon atoms.

In the general formula [IV], Y represents a group of non-metallic atoms necessary for forming a monocyclic or condensed 5- to 7-membered heterocyclic ring together with N. Examples of heterocycles formed by N and Y include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole,
Benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide, saccharin, oxazolidine-2,4-dione, imidaziridine-
2,4-dione, thiazolidine-2,4-dione, urazole, parabanic acid, maleimide, 2-pyridone, 4-
Pyridone, 6-pyridazone, 6-pyrimidone, 2-pyrazone 1,3,5-triazin-2-one, 1,2,4-triazin-6-one, 1,3,4-triazin-6-one, 2, -Oxazolone, 2-thiazolone, 2-imidazolone, 3-isoxazolone, 5-tetrazolone, 1,2,4-triazo-5-one and the like, which may be substituted,
Examples of the substituent include a halogen atom, a hydroxyl group,
Nitro group, cyano group, hydroxy group, aliphatic group, aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group,
Carbonamido group, sulfoamido group, carbamoyl group,
Examples include a sulfamoyl group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, and a substituted amino group.

In the present invention, the aliphatic group represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of the aliphatic group include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, t
-Butyl group, t-amyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n
-Decyl group, n-dodecyl group, n-tetradecyl group, n
-Hexadecyl group, 2-hexyldecyl group, n-octadecyl group, allyl group, benzyl group, phenethyl group, undecenyl group, octadecenyl group, trifluoromethyl group, chloroethyl group, cyanoethyl group, 1- (ethoxycarbonyl) ethyl group, Examples include a methoxyethyl group, a butoxyethyl group, a 3-dodecyloxypropyl group, and a phenoxyethyl group. In the present invention, the heterocyclic group is a substituted or unsubstituted monocyclic or condensed-ring heterocyclic group. 2-furyl, 2-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, oxazole-
2-yl group, thiazol-2-yl group, benzoxazol-2-yl group, benzothiazol-2-yl group, 1,
There are a 3,4-thiadiazol-2-yl group, a 1,3,4-oxadiazol-2-yl group and the like. In the present invention, the aromatic group is a substituted or unsubstituted monocyclic or condensed-ring aryl group, for example, phenyl, tolyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2 -Naphthyl group, 4-t-butylphenyl group and the like.

Next, examples of preferred substituents in the coupler represented by the general formula [I] used in the present invention will be described. ^RI is preferably an aliphatic group (methyl, ethyl, n-propyl, t-
Butyl, etc.), aliphatic oxy group (methoxy, ethoxy, n
-Butoxy, n-dodecyloxy, etc.), a halogen atom (fluorine, chlorine, bromine), a carbonamide group (acetamide, n-butanamide, n-tetradecaneamide, benzamide, etc.) or a sulfonamide group (methanesulfonamide, n- Butanesulfonamide, n-octanesulfonamide, n-dodecanesulfonamide group, toluenesulfonamide, etc.). R ^II is preferably a chlorine atom or an aliphatic oxy group (methoxy, ethoxy, methoxyethoxy, n-octyloxy, 2-ethylhexyloxy, n-tetradecyloxy, etc.). R ^III is preferably other aliphatic oxycarbonyl group (methoxycarbonyl substituent groups listed in the R ^I, ethoxycarbonyl, n- butoxycarbonyl, n- hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-
(Ethoxycarbonyl) ethyloxycarbonyl, 3-
Dodecyloxypropyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, phenethyloxycarbonyl and the like or a carbamoyl group (dimethylcarbamoyl, dibutylcarbamoyl, dihexylcarbamoyl, di-2-ethylhexcarbamoyl, n-dodecyl) Carbamoyl and the like). m is preferably 0 to 2, and n is preferably 0 to 2. X is preferably a group of the general formula [II] wherein R ^IV is an aromatic group (4-methoxycarbonylphenoxy, 4-methanesulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamide-4
-Ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy, etc.) or a group represented by the general formula [IV], and of the latter, a group represented by the following general formula [V] More preferred.

General formula [V] In the general formula [V], V represents a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group, or a substituted or unsubstituted imino group. Where V
Is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by the general formula [V] include a succinimide group, a phthalimide group, a 1-methyl-imidazolidin-2,4-dione-3-yl group, and a 1-benzyl-imidazolidin-2,4 -Dion-3-yl group, 5-ethoxy-1-methylimidazolidin-2,4-dione-3-yl group, 5-hexyloxy-1-methylimidazolidin-2,4-dione-3-yl group , 5-methoxy-1-methylimidazolidine-2,4-dione-3-yl group, 5-butoxy-1-methylimidazolidin-2,4-dione-3
-Yl group, 5,5-dimethyloxazolidine-2,4-dione-3-yl group, thiazolidine-2,4-dione-3-yl group, 1-benzyl-2-phenyltriazolidine-3,5
-Dion-4-yl group, 1-n-propyl-2-phenyldriazolidine-3,5-dione-4-yl group, 5-ethoxy-1-benzyl-imidazolidin-2,4-dione- There is a 3-yl group and the like.

The yellow coupler represented by the general formula [I] may have any of the substituents R ^I , R ^II , R ^III or X as a divalent to tetravalent coupler by forming a divalent to tetravalent linking machine. Good, but monomers or dimers are preferred. Here, when the yellow coupler represented by the general formula [I] is a dimer to a tetramer, the carbon number range mentioned for R ^I , R ^II , R ^III or X serving as a linking group is not limited thereto.

Specific examples of the yellow coupler represented by the general formula [I] used in the present invention are shown below, but the coupler used in the present invention is not limited thereto. The equivalent molecular weight of each coupler is shown in parentheses.

The yellow coupler used in the present invention is synthesized by a conventionally known method. For example, U.S. Pat.
7,554, 3,408,194, 3,415,652, 3,447,928
No. 4,401,752, UK Patent 1,040,710, JP 47-26
No. 133, No. 47-37736, No. 48-733147, No. 48-94432
No. 48-68834, No. 48-68835, No. 48-68836,
No. 50-34232, No. 51-50734, No. 51-102636, No. 55
-598, 55-161239, 56-95237, 56-1615
No. 43, No. 56-153343, No. 59-174839 and No. 60-3573
It can be synthesized by the synthesis method described in the specification of No. 0. Next, typical examples of synthesis of the coupler used in the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (Y-2) α- (p-methoxybenzoyl) -2-chloro-5-
54 g of (1-ethoxycarbonylethyloxycarbonyl) acetanilide was suspended in 200 ml of chloroform, and 20.1 g of bromine was added dropwise at room temperature. After stirring for 1 hour, the reaction mixture was washed twice with 100 ml of water and dried over Na ₂ SO ₄ .

Then, had a Na ₂ SO _4, at room temperature the solution, 5-ethoxy-1-benzyl-2,4-dione 70 g,
3 in a solution of 33.4 ml of triethylamine and 200 ml of chloroform
Added at 0 minutes. After 3 hours, the reaction solution was mixed with 200 ml of water and 1N-NaOH aqueous solution.
150 ml × 2 times, 0.5N-HCl water 200 ml × 2 times, saturated saline 200
After washing with ml, it was dried over Na ₂ SO ₄ . The chloroform layer is concentrated, and the residue is subjected to a silica gel column (hexane: ethyl acetate =
2: 1) and the desired compound (Y
-2) was obtained in an amount of 71 g (oil).

The structure was confirmed by mass spectrometry spectrum; H-NMR spectrum and elemental analysis.

m / e; 679 (M ⁺ ) Elemental analysis,% CHN Observed 60.27 5.12 6.14 Calculated 60.04 5.04 6.18 Synthesis Example 2 Synthesis of exemplified compound (Y-18) α- (p-methoxybenzoyl) -2-chloro- 5-
64 g of octyloxycarbonylacetanilide was brominated in the same manner as in Synthesis Example 1 above (chloroform 250 ml, B
_{r 2 23.5g), No 2 SO} 4 dried, filtered. The solution was treated with 82 g of 5-ethoxy-1-benzylimidazolidine-2,4-dione,
A solution of triethylamine (39 ml) and chloroform (250 ml) was added dropwise at room temperature.

After 3 hours, the reaction mixture was post-treated in the same manner as in the above Synthesis Example, and concentrated under reduced pressure. The residue was crystallized from 250 ml of methanol to obtain 69 g of the desired compound (mp. 98-9 ° C).

m / e; 691 (M ⁺ ) Elemental analysis% CHN Found 64.25 6.17 6.06 Calculated 64.19 6.12 6.07 Synthesis example 3 Synthesis of exemplified compound (Y-19) α- (p-methoxybenzoyl) -2-chloro-5 −
Octyloxycarbonyl acetanilide 46 g, Br ₂ 16.8
g and chloroform (250 ml) in the same manner as in the above Synthesis Example.
A solution of 49.5 g of 1-methylimidazolidine-2,4-dione, 28 ml of triethylamine and 200 ml of chloroform was added dropwise at room temperature. After 3.5 hours, the mixture was worked up in the same manner as in the above Synthesis Example and concentrated. The residue was crystallized from 300 ml of ethanol to obtain the target compound as white crystals (43 g, mp. 79-80 ° C).

m / e; 671 (M ⁺ ) Elemental analysis% CHN Actual value 62.69 6.98 6.21 Calculated value 62.53 6.90 6.25 Two or more yellow couplers of the general formula (I) may be used, or in combination with a yellow coupler outside the present invention. May be.

The yellow coupler of the formula (I) used in the present invention is contained in a photosensitive silver halide emulsion layer and an adjacent layer.

The total amount of the coupler of the present invention is 0.02 to 3.0 g /
m ^2, preferably more preferably 0.1 to 1.5 g / m ² 0.2 to 1.0 g /
a m ^2.

The amount of the high boiling point organic solvent to be added to the yellow coupler-containing layer of the general formula (I) is at most 0.5 by weight, preferably at most 0.1, relative to all the yellow couplers contained in the yellow coupler-containing layer. To 0.35, more preferably 0.1 to 0.3, but may be 0.

The above all yellow couplers also include yellow couplers that release a photographically useful group, such as development inhibitor releasing couplers.

The high-boiling organic solvent referred to in the present invention is a water-immiscible solvent having a boiling point of 175 ° C. or more at normal pressure.

As the high-boiling organic solvent to be added to the yellow coupler-containing layer of the formula (I), known organic solvents are used. For example, phosphates (tricresyl phosphate, triphenyl phosphate, dioctyl butyl phosphate, tri-n-hexyl phosphate, tricyclohexyl phosphate, trioctyl phosphate, etc.), phthalic acid Esters (eg, dibutyl sterate, dioctyl phthalate, dicyclohexyl phthalate, didodecyl phthalate), citrates (eg, tributyl acetyl citrate), alkylamides (eg, diethyl laurylamide), benzoates (eg, octyl benzoate) ), Fatty acid esters (eg, dibutoxyethyl succinate,
Diethyl azelate), trimesic esters (eg, tributyl trimesate) and the like.

As a method for adding these high-boiling organic solvents, a yellow coupler and these high-boiling organic solvents are so-called low-boiling organic solvents having a boiling point of 30 to 150 ° C (for example, lower alkyl acetates such as ethyl acetate and butyl acetate, and ethyl propionate). Secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methylcellosolve acetate, etc.) and then emulsified and dispersed in a hydrophilic colloid. Further, another emulsified dispersion of a single high-boiling organic solvent may be prepared and added to the single dispersion of the yellow coupler.

 Next, the processing of the present invention will be described in detail.

In the case of a color photographic material for photographing, for example, a color negative film, about 1200 ml of a color developing replenisher is usually replenished per 1 m ^{2 of} the film in the color developing process. In fact, with such a replenishment amount, even in the case of a considerably small amount of processing and a condition in which the processing amount fluctuates, a problematic fluctuation in processing performance hardly occurs. However, the replenishment volume is 700ml
When reduced to the following, the problem increases significantly. Such changes in performance are caused by higher gradation and fog density due to evaporation and concentration of the developing solution, softer gradation and lower fog density due to oxidation of the color developing agent, and fluctuations in processing amount. High or low tone gradation and increase or decrease in fog density due to the increase or decrease in the bromine ion concentration are superimposed on each other, giving an extremely complicated appearance. Here, the gradation is hardened in any of yellow, magenta and cyan, but is particularly remarkable in yellow.
Therefore, hitherto, no solution has been found for this problem.

However, the present inventors have remarkably improved the above problems by using a yellow coupler represented by the above general formula (I) in a light-sensitive material and a high-boiling organic solvent in the above-described ratio in the yellow coupler-containing layer. is, 1m ² per 200ml
It has been found that a stable processing result can be obtained even with a replenishing amount of 500 ml or less.

The color developing agents used in the color developing solution and the color developing replenisher are aromatic primary amine compounds, including known compounds widely used in various color photographic processes. However, in the present invention, preferred color developing agents are (1) 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate (2) 4- (N-ethyl-N-β- Methanesulfonamidoethylamino) -2-methylaniline sulfate (3) 4- (N-ethyl-N-β-methoxyethylamino) -2-methylaniline-p-toluenesulfonate (4) 4- (N , N-Diethylamino) -2-methylaniline hydrochloride (5) 4- (N-ethyl-N-dodecylamino) -2
-Methylaniline sulfate (6) N, N-dialkyl-p-phenylenediamine-based color developing agents such as N, N-diethyl-p-phenylenediamine hydrochloride. These compounds are present in the color developer at 0.00
It is added in the range of 5-0.05 mol /, preferably 0.0
1-0.04 mol /, particularly preferably 0.015-0.03 mol /
Range. Further, it is preferable to add the replenisher for color development so as to have a higher concentration than the above concentration. Specifically, how high the concentration should be depends on the setting of the replenishment amount. However, in general, 1.05% of the color developing solution (mother liquor) is used.
2.0 times, more often in the range of 1.2-1.8 times.

The color developing agents may be used alone or in combination depending on the purpose. Preferred examples of the combination include (1) and (2), (1) and (3), and (2) and (3) among the above color developing agents.

In the present invention, the bromine ion concentration of the color developing solution is 0.00
The content is preferably in the range of 5 to 0.02 mol /. For this purpose, the bromide content of the replenisher is preferably set to 0.005 mol / or less. In general, the lower the replenishment rate, the lower the bromide content in the replenisher should be set,
In particular, in the present invention, it is preferable that the replenisher does not contain bromide in order to greatly reduce the replenishment amount.

The bromide includes potassium bromide, sodium bromide, lithium bromide, hydrobromic acid and the like.

The color developing solution and the color developing replenisher include hydroxylamine, diethylhydroxylamine, triethanolamine, compounds described in West German Patent (OLS) No. 2622950, compounds described in Japanese Patent Application No. 61-265149, sulfites, and the like. And preservatives such as bisulfite.

In addition, various chelating agents are also added for the purpose of softening water and hiding a metal. In the present invention, at least one of the compounds represented by the following general formulas (II), (III) and (IV) is used. It is preferable to include them.

In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represents a hydrogen atom,
Represents an alkali metal atom or ammonium.

R is particularly preferably a methyl group or an ethyl group.
Is preferably a hydrogen atom or a sodium atom.
The compound has an effect of suppressing a change in gradation and fog density particularly in low replenishment processing of a color light-sensitive material containing a yellow coupler of the general formula (I).

Accordingly, the present invention can be carried out more effectively by incorporating at least one of the compounds of the general formulas (II), (III) and (IV) into the color developer and the color developer replenisher. You.

In particular, it is more preferable to use one or more of the compounds represented by (II) and (III) or (II) and (IV) in combination.

Specific examples of the compounds represented by formulas (II), (III) and (IV) are described below.

The compound of the general formula (II) is added to the color developer and its replenisher in the range of 0.0005-0.02 mol /, preferably
0.001-0.01 mol / added. Also, the general formula (III),
The compound (IV) is similarly added in the range of 0.002 to 0.1 mol /, preferably 0.005 to 0.05 mol /.

When the compounds of the general formulas (II) and (III) or (II) and (IV) are used in combination, the compound of (II) is (III) or (IV)
2 to 20 times, preferably 3 to 15 times, the molar ratio of the compound
2 times, more preferably 3-10 times.

Among the above specific examples, (II-1) and (III-
It is preferable to use 1), (II-1) and (IV-1) together.

In the color developing solution used in the present invention, in addition to the above compounds, a pH buffer such as an alkali metal carbonate, borate or phosphate; iodide, benzimidazoles, benzothiazoles, mercapto compounds Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines, thiocyanate; nucleating agents such as sodium borohydride; Auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; and formulas (II), (III) and (I
In addition to the compound represented by V), ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, and Research Disclosure 18
Various chelating agents such as the organic phosphonic acids described in No. 170 (May 1979) can be used alone or in combination.

In the present invention, the pH value of the color developing solution and its replenisher is usually 9 or more, preferably 9.5-12, particularly preferably 9.5-11.0. In the above range, the replenisher for the color developer is preferably set to a value higher by about 0.05 to 0.3.

Further, the temperature in the color development process is 30-45 ° C., and it is preferable that the temperature is constant to achieve a larger low replenishment process, and in the present invention, the temperature is 35-45 ° C., especially
It is preferably carried out at 38-42 ° C.

The present invention can be carried out in any of an automatic developing machine and manual processing, but is preferably carried out in an automatic developing machine. In the processing of the automatic developing machine, the number of color developing solution tanks may be one or more. However, if a plurality of tanks are used and a multi-stage forward replenishing method in which the front tank is replenished and sequentially flows into the rear tank is used, the replenishment is further reduced. be able to. It is preferable that the contact area between the developer and the air in the tank is as small as possible. Specifically, a floating lid, a seal with a liquid having a high boiling point and a specific gravity smaller than that of the developer, Japanese Patent Application No. 61-278283
The use of shielding means such as a tank structure in which the opening is narrowed as described in 1) further enhances the effects of the present invention.

Further, as a means for enhancing the effect of the present invention, it is preferable to replenish water according to the amount of evaporation in order to correct the evaporation and concentration of the developer. The water to be replenished is preferably deionized water that has been subjected to an ion exchange treatment or deionized water that has been subjected to a treatment such as reverse osmosis or distillation.

The color developing solution and the color developing replenisher are prepared by sequentially adding and dissolving the above-mentioned chemicals in a certain amount of water, and the above-mentioned deionized water is preferably used as the preparation water.

In the present invention, the photosensitive material after color development is a bleaching solution,
Alternatively, it is processed with a bleach-fix solution. As a bleaching agent used in these, a chain salt of ferric ion and a chelating agent such as aminopolycarboxylic acid, polycarboxylic acid, aminopolyphosphonic acid and the like is generally used. Examples of preferred chelating agents used as complex salts with these ferric ions include (1) ethylenediaminetetraacetic acid (2) diethylenetriaminepentaacetic acid (3) cyclohexanediaminetetraacetic acid (4) 1,3-diaminopropanetetraacetic acid ( 5) Nitrilotriacetic acid (6) Iminodiacetic acid (7) Glycol ether diaminetetraacetic acid, etc., but not limited thereto.

The ferric ion complex salt may be used in the form of a complex salt, or a ferric salt such as ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, ferric phosphate and the like. A ferric ion complex salt may be formed in a solution using a chelating agent such as polycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid. When used in the form of a complex salt, one kind of complex salt may be used, or two or more kinds of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Further, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of forming the ferric ion complex salt. Of the iron complexes, iron aminopolycarboxylate iron complexes are preferable, and the amount of addition is 0.1 to 1 mol /, preferably 0.2 to 0.4 mol / in a bleaching solution of a color photographic light-sensitive material for photography such as a color negative film. In the bleach-fix solution, it is 0.05 to 0.5 mol /, preferably 0.1 to 0.5 mol /.
~ 0.3 mol /. In a bleaching solution or a bleach-fixing solution of a color photographic light-sensitive material for printing such as color paper, the amount is 0.03 to 0.3 mol /, preferably 0.05 to 0.2 mol /.

In the bleaching solution or the bleach-fixing solution, a bleaching accelerator can be used if necessary. As specific examples of useful bleaching accelerators, compounds having a mercapto group or a disulfide group are preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention may contain bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Addition of one or more inorganic acids and organic acids having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The above-mentioned bleaching agent is usually used in the range of pH 4 to 7, preferably 4.5 to 6.5, particularly preferably 5 to 6.3. The pH of the bleach-fix solution is 4 to 9, preferably 5 to 8, particularly preferably 5.5 to 7.5. When the pH is higher than the above range, bleaching failure tends to occur, and when the pH is lower, poor coloring of the cyan dye tends to occur.

The fixing agent used in the bleach-fixing solution of the present invention or the fixing solution used after processing with the bleaching solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate, ammonium thiocyanate Thiocyanates such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol and water-soluble silver halide solubilizers such as thioureas; Two or more kinds can be used as a mixture. Also, JP-A-51-1553
A special bleach-fixing solution comprising a combination of the fixing agent described in No. 54 with a large amount of a halide such as potassium iodide or the like can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per one is preferably 0.3 to 2 mol, and particularly in the processing of a color photographic light-sensitive material for photography, 0.8 to 1.5 mol.
In the processing of a color photographic light-sensitive material for printing, the range is 0.5 to 1 mole.

The pH range of the fixing solution in the present invention is preferably from 4 to 9,
Particularly, 5 to 8 is preferable. If the pH is lower than this, the solution is remarkably deteriorated, and if the pH is higher than this, ammonia volatilizes from the ammonium salt contained and stains are easily generated.

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

The bleach-fixing solution or fixing solution used in the present invention may be a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) or a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. And a metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / in terms of sulfite ion, more preferably 0.04 to 0.50 mol.
0.40 mol /.

As a preservative, the addition of sulfite is common,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, a fluorescent whitening agent, a chelating agent, a fungicide, and the like may be added as necessary.

As described above, the photosensitive material after color development is processed with a bleaching solution, a bleach-fixing solution, and a fixing solution. If the pH of the processing solution after color development is 6 or more, the squeegee of an automatic developing machine to be used is used. If the image quality is poor, yellow fog may occur, but the present invention has an advantage that such a problem is reduced.

That is, the present invention is also preferably practiced when processing in a processing solution having a pH of 6 or more after color development.

After the fixing step or the bleach-fixing step, it is common to perform processing steps such as water washing and stabilization, such as performing only water washing or performing only a stable processing step without providing a substantial water washing step. A simple processing method can be used.

The washing step is to remove processing solution components adhered or occluded on the color photographic material or unnecessary components in the color photographic material, thereby improving image storability and film physical properties after processing. Acts as a preservative.

On the other hand, the stabilizing step is a step of improving the storability of an image to a level that cannot be obtained by washing with water.

The rinsing step may be performed in one tank, but is often performed by a multi-stage countercurrent rinsing method of two or more layers. The amount of water in the rinsing step can be arbitrarily set according to the type and purpose of the color photographic material. For example, the Journal of Motion Picture and Television Engineering, Vol. 64, pp. 248-253 (May, 1955) No.)
Slow Rate in Imajyon Watching of Motion Picture Film "Water Flow Rates in
Immersion-Washing of Motion Picture Film, SRGol
dwasser) can also be used.

When the amount of washing water is reduced, the generation of bacteria and mold becomes a problem, but as a countermeasure, it is preferable to use washing water in which calcium and magnesium are reduced as described in Japanese Patent Application No. 61-131632. Also disinfectants and deterrents, such as the Journal of Antibacterial
And Anfunningal Age (J. Antibact.A
ntifug. Agents), vol. 11, No. 5, p. 207-223 (1983) and compounds described in Hiroshi Horiguchi, "Chemistry of Bacterial and Fungicide Protection"). Further, as a water softener, a chelating agent such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can be added.

When the amount of washing water is reduced, the amount of water is usually 100 ml / 2000 ml / m ^{2 of the} color photographic material, and particularly preferably in the range of 200 ml to 1000 ml from the viewpoint of achieving both color image stability and water saving effect.

The pH in the washing step is usually in the range of 5-9. In addition, various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers for adjusting the membrane pH after the treatment (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
Ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. may be used in combination), the same chelating agent that can be added to the washing water, a bactericide, and other fluorescent whitening agents according to the intended use. And various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, ammonium thiosulfate, and the like.

The pH of the stabilizing bath is usually 3 to 8, but a low pH range of 3 to 5 may be preferably used depending on the kind of the light-sensitive material and the purpose of use.

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

The silver halide emulsion used in the present invention is a research-based silver halide emulsion.
Day Closure, vol.176, Item No.17643, [I]
It can be prepared using the method described in the section.

The silver halide color photographic light-sensitive material used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. In the case of a high-sensitivity light-sensitive material, silver iodobromide (3 to 20 mol% of silver iodide) is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron and rhombic dodecahedron may be used, and those having regular crystal forms such as spheres and those having crystal defects such as twin planes Alternatively, a composite form thereof may be used.

The silver halide grains may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a monodisperse emulsion having a wide distribution. Typical monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, of which at least about 95% by weight is within ± 40% of the average grain diameter. Emulsions having an average grain diameter of about 0.25 to 2 microns and having at least about 95% by weight or at least about 95% by number of silver halide grains within the average grain diameter ± 20% can be used in the present invention. .

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in British Patent 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and JP-A-60
No. 143331. Further, silver halides having different compositions may be joined by an epitaxial junction.

By using tabular grains in the silver halide photographic emulsion used in the present invention, it is possible to improve the sensitivity including the efficiency of color publication by a sensitizing dye, improve the relationship between sensitivity and granularity, improve the sharpness, and develop. Improvement of progression, 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, those having a diameter of more than 8 and those having a diameter / thickness of 5 or more and 8 or less.

The tabular grains may have a uniform halogen composition or may have two or more phases having different halogen compositions. For example, when silver iodobromide is used, the silver iodobromide tabular grains each having a layered structure composed of a plurality of phases having different iodide contents can be used. JP-A-58-113928 and JP-A-59-99433 describe preferred examples of the halogen composition and the distribution of halogen in the tabular silver halide grains.

The preferred method of using the tabular silver halide grains in the present invention is Research Disclosure No. 225
34 (January 1983) and No. 25330 (May 1985), which disclose methods of use based on, for example, the relationship between tabular grain thickness and optical properties. .

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method. For example, Research Disclosure (RD), No. 17643 (December, 1978), pp. 22-23, "I. Emulsion Production ( Emulsion preparation and types) ”and
No. 18716 (November 1979), p.648, the method can be followed.

Various photographic additives that can be used in the present invention are described, for example, in Research Disclosure No. 17643, pages 23 to 28, and No. 18716, pages 648 to 651. The types of these additives and their detailed locations are shown below: Various color couplers can be used for the light-sensitive material that can be used in the processing of the present invention. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized form of an aromatic primary amine developer.
Typical examples of useful color couplers are naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. These cyan, which can be used in the present invention,
Specific examples of magenta and yellow couplers
Day Closure (RD) 17643 (December 1978) VII-D
And in the patents cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is diffusion-resistant by being polymerized. A bi-equivalent coupler substituted with a coupling-off group is more preferable than a tetra-equivalent coupler of a hydrogen atom at the coupling active position in that the coated silver amount can be reduced. Further, couplers in which the color-forming dye has an appropriate diffusibility, colorless couplers, or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator can also be used.

As a yellow coupler that can be used in combination with the yellow coupler represented by the general formula (I) in the present invention, an oil-protected acylacetamide-based coupler is a typical example. A specific example is described in U.S. Pat.
No. 0, 2,875,057 and 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferable, and U.S. Patent Nos. 3,408,194 and 3,447,9
No. 28, Nos. 3,933,501 and 4,022,620, etc., and an oxygen atom-elimination type yellow coupler or JP-B-58-10739, U.S. Pat.Nos. 4,401,752, 4,326,
024, RD18053 (April 1979), UK Patent No. 1,425,020
No. 2,219,917, No. 2,261,361, No. 2,329,587 and No. 2,433,812, of which nitrogen atom-elimination type yellow couplers are mentioned as typical examples. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color density.

Examples of the magenta coupler that can be used in the present invention include oil-protected, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based, and pyrazoloazole-based couplers such as pyrazolotriazoles. 5-pyrazolone couplers are preferably couplers 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 a coloring dye, and typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,343,703. No. 2,600,788, No. 2,908,573, No. 3,062,653,
Nos. 3,152,896 and 3,936,0.15. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is particularly preferable. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in JP 061,432, preferably pitizolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) ) And JP-A-60-3
And pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. The imidazo [1,2-) described in U.S. Pat.No.4,500,630 in terms of low yellow side absorption and light fastness of the coloring dye.
b] pyrazoles are preferred, and pyrazolo [1,5-b] [1,2,4] triazole described in U.S. Pat. No. 4,540,654 is particularly preferred.

Further, as the magenta coupler, preferably, a two-equivalent magenta coupler of pyrazole separation described in U.S. Pat.No. 4,367,282 and U.S. Pat.
An arylthio-eliminating 2-equivalent magenta coupler described in 4,522,915 or the like is used in combination.

Cyan couplers 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.Nos. 4,052,212, 4,146,396, and
Representative examples thereof include oxygen atom-eliminating double-equivalent naphthol couplers described in 4,228,233 and 4,296,200. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929, 2,801,171, and 2,772,16.
No. 2, No. 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, and typical examples are U.S. Pat.
Phenol cyan couplers having an alkyl group at the meta-position of the phenol nucleus described above in No. 002 described in U.S. Pat.No. 2,772,162, U.S. Pat.
126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365, etc.
And phenolic couplers containing a phenylureido group at the 2-position and having an acylamino group at the 5-position, and the like, described in JP-A Nos. 4,451,559 and 4,427,767. Japanese Patent Application Nos. 59-93605, 59-264277 and 59-268
Cyan couplers described in No. 135 wherein a 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in color image fastness and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength region of the dye formed from the magenta and cyan couplers, it is preferable to use a colored coupler together with a color negative photosensitive material for photography. U.S. Pat.No. 4,163,670 and JP-B-57-394
Typical examples thereof include a yellow-colored magenta coupler described in No. 13 and the like and a magenta-colored cyan coupler described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blurred couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,5.
No. 70 has a specific example of a magenta coupler, and EP 9
No. 6,570 and German Offenlegungsschrift 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of the polymerized magenta coupler are described in UK Patent No. 2,102,173, U.S. Patent No. 4,367,282, Japanese Patent Application Nos. 60-75041 and 60-750.
113596.

Various couplers can be used in combination of two or more in the same layer of the photosensitive layer, or the same compound can be introduced in two or more different layers in order to satisfy the characteristics required for the photosensitive material. .

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

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

Examples of the DIR coupler include those which release a heterocyclic mercapto-based development inhibitor described in, for example, US Pat. No. 3,227,554; and those which release a benzotriazole derivative as a development inhibitor described in JP-B-58-9942; Kuniaki 51-16
No. 141, etc., so-called non-colored DIR couplers;
No.-90932, which releases a nitrogen-containing heterocyclic development inhibitor accompanied by decomposition of methylol after leaving; US Pat.
No. 4,248,962 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after elimination; JP-A-61-114946, JP-A-57-154234, and JP-A-57-188035. issue,
No. 58-98728, No. 58-209736, No. 58-209737, No. 5
Nos. 8-209738, 58-209739, and 58-209740, which release a development inhibitor by electron transfer through a conjugated system after leaving; Japanese Patent Application Laid-Open Nos. 57-151944 and 58-209740.
No. 2,179,32, etc., which release a diffusible development inhibitor whose development inhibiting ability is deactivated in the present solution; Japanese Patent Application Nos. 59-38263, 5
No. 9-39653, which release a reactive compound and generate a development inhibitor by in-film reaction during development or deactivate the development inhibitor.
Among the DIR couplers described above, those which are more preferable in combination with the present invention are those inactivated with a developer represented by JP-A-57-151944: U.S. Pat. No. 4,248,962 and JP-A-57-151944.
Timing type represented by −154234; Japanese Patent Application No. 59-3965
Reaction types represented by No. 3, particularly preferred among them are JP-A-57-151944, JP-A-58-217932, and JP-A-58-217932.
No. 218644, JP-A-60-225156 and JP-A-60-233650.
It is a reactive DIR coupler described in 9653 and the like.

As the photosensitive material that can be used in the present invention, a compound that releases an image-forming nucleating agent or a development accelerator or a precursor thereof (hereinafter, referred to as “development accelerator or the like”) during development may be used. it can. Typical examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188, which release a development inhibitor and the like by a coupling reaction with an oxidized aromatic primary amine developer. A coupler, that is, a DAR coupler.

It is preferable that the development accelerator and the like released from the DAR coupler have an adsorptive group to silver halide. Specific examples of such a DAR coupler are described in JP-A-59-157638 and JP-A-59-170840. No. A DAR which forms an N-acyl-substituted hydrazine having a monocyclic or condensed heterocyclic ring as an adsorptive group, which is released from a coupling active position of a photographic coupler with a sulfur atom or a nitrogen atom.
Couplers are particularly preferred, and specific examples of such couplers are described in JP-A-60-128446.

Compounds described in JP-A-60-37556 having a development accelerator moiety in a coupler residue, or JP-A-60-1007029 releasing a development accelerator or the like by an oxidation-reduction reaction with a developing agent. Can also be used in the light-sensitive material of the present invention.

The DAR coupler is preferably introduced into a light-sensitive silver halide emulsion layer of a light-sensitive material.
It is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers as described in JP-A No. 60-128429.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

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

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 A multilayer color light-sensitive material 101 was prepared by applying a total of each of the following compositions on a subbed cellulose triacetate film support.

(Composition of photosensitive layer) The number for each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver.
However, with respect to the sensitizing dye and the coupler, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer: anti-halation layer Black colloidal silver: silver 0.18 Gelatin: 1.40 Second layer: intermediate layer 2,5-di-t-pentadecylhydroquinone: 0.18 C-1: 0.07 C- 3 ... 0.02 U-1 ... 0.08 U-2 ... 0.08 HBS-1 ... 0.10 HBS-2 ... 0.02 Gelatin ... 1.04 Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion (iodide) 6 mol% silver, average particle size 0.8μ)
Silver 0.50 Sensitizing dye IX ... 6.9 x ^10-5 Sensitizing dye II ... 1.8 x ^10-5 Sensitizing dye III ... 3.1 x ^10-4 Sensitizing dye IV ... 4.0 x ^10-5 C-2 ... 0.146 HBS-1 0.005 C-10 0.015 Gelatin 1.20 4th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.85 μm)
Silver 1.15 Sensitizing dye IX ... 5.1 x ^10-5 Sensitizing dye II ... 1.4 x ^10-5 Sensitizing dye III ... 2.3 x ^10-4 Sensitizing dye IV ... 3.0 x ^10-5 C-2 ... 0.060 C-3 0.008 C-10 0.008 HBS-1 0.005 Gelatin 1.50 Fifth layer; Third red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size) 1.5μ) ......
Silver 1.50 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 C-5 ... 0.012 C-3... 0.003 C-4... 0.004 HBS-1... 0.32 Gelatin... 1.63 6th layer; Intermediate layer Gelatin... 1.06 7th layer; 1st green sensitive emulsion layer Silver iodobromide emulsion ( (Silver iodide 6 mol%, average grain size 0.8μ) ......
Silver 0.35 Sensitizing dye V: 3.0 × 10 ^-5 Sensitizing dye VI: 1.0 × 10 ^-4 Sensitizing dye VII: 3.8 × 10 ^-4 C-6: 0.120 C-1: 0.021 C-7 0.030 C-8 0.025 HSB-1 0.20 Gelatin 0.70 Eighth layer; Second green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.85 μm)
Silver 0.75 Sensitizing dye V ... 2.1 x ^10-5 Sensitizing dye VI ... 7.0 x ^10-5 Sensitizing dye VII ... 2.6 x ^10-4 C-6 ... 0.021 C-8 ... 0.004 C-1 0.002 C-7 0.003 HSB-1 0.15 Gelatin 0.80 Ninth layer; Third green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5 μm)
Silver 1.80 Sensitizing dye V: 3.5 × 10 ^-5 Sensitizing dye VI: 8.0 × 10 ^-5 Sensitizing dye VII: 3.0 × 10 ^-4 C-6: 0.011 C-1: 0.001 HBS-2 0.69 gelatin ... 1.74 10th layer; yellow filter layer Yellow colloidal silver ... silver 0.05 2,5-di-t-pentadecylhydroquinone ... 0.03 gelatin ... 0.95 11th layer; first blue-sensitive emulsion layer Silver bromide emulsion (silver iodide 6 mol%, average grain size 0.6μ) ......
Silver 0.24 Sensitizing dye VIII… 3.5 × 10 ^-4 Cp-1 0.27 C-8… 0.005 HBS-1… Amount described in Table-3 Gelatin …… 1.28 12th good; 2nd blue-sensitive emulsion layer Silver bromide emulsion (silver iodide 10 mol%, average grain size 1.0μ) ......
Silver 0.45 Sensitizing dye VIII... 2.1 × 10 ^-4 Cp-1 0.098 HBS-1... Amount described in Table-3 Gelatin... 0.46 13th layer; 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Iodine) 10 mol% silver halide, average particle size 1.8μ)
Silver 0.77 Sensitizing dye VIII ...... 2.2 × 10 ^-4 C-9 0.036 HBS-1 ...... 0.07 Gelatin ...... 0.69 14th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size) 0.07μ) ... silver 0.
5 U-1 ... 0.11 U-2 ... 0.17 HBS-1 ... 0.90 15th layer; 2nd protective layer Polymethyl methacrylate particles (diameter about 1.5 m) 0.2
... 0.54 S-1... 0.15 S-2... 0.10 Gelatin... 0.72 In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

The coupler Cp-1 of the eleventh layer and the twelfth layer of the sample 101 was emulsified and dispersed as follows and added.

Dissolve 80 g of Cp-1 and 80 g of HBS-1 in 200 cc of ethyl acetate,
It was mixed with 1000 g of 10% gelatin containing 1 g of sodium dodecylbenzenesulfonate and emulsified and dispersed with a homogenizer for 10 minutes.

(Samples 102 to 124) Cp-1 in the eleventh and twelfth layers of Sample 101 was replaced with the coupler shown in No.-3 in an equimolar amount, and HBS-1 was replaced with Table 1.
3, and the amount of gelatin applied was changed in order to equalize the film quality of each raw sample. The film quality is 0.1
Scratch strength with μ diamond needle and relative humidity 70% at 60 ° C, 7
It was adjusted by the sweating phenomenon after a day.

After cutting the sample 101-124 produced as described above to a width of 35 mm, this was exposed to a 4800 ° K, 20CMS wedge,
Each was processed by an automatic processor according to the steps described in Table 1. This was designated as S1. Next, the sample 101 cut to a width of 35 mm was put into a camera and exposed, and then, in the process No. 1-4 shown in Table 2, the accumulated replenishment amount of the color developing replenisher was 20 m / day, 20 m a day. Until it reached.

In the above table, the replenishment amount is per 1 m ² of the photosensitive material.

The composition of the processing solution used is described below.

(Washing solution) Common for mother liquor and replenisher Tap water is filled with H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type anion exchange resin (Amberlite IR-400) Water was passed through the bed column to treat the calcium and magnesium ion concentrations at 3 mg / or less, and then 20 mg / sodium dichloride isocyanurate and sodium sulfate were added.

 This solution had a pH in the range of 6.5-7.5.

During the processing, samples 101-124 were given the same wedge exposure as described above, and were processed once each day,
S3 ……… Sn.

For Samples 101 to 124, the maximum gradation difference and the maximum fog density difference among S1 to Sn were calculated, and are shown in Table 3 as representative values of the processing fluctuation.

Here, the fog density is a density obtained by processing an unexposed sample from development to the final step.

The tone is calculated from the exposure point that gives the minimum density + 0.2 density and the density corresponding to the exposure amount obtained by adding 1.5 as a logarithmic value of the exposure amount (lux / sec). The value was obtained by subtracting +0.2.

 The results are shown in Table-3.

In Table 3, the numerical value in the box in the column of the coupler indicates the molecular weight.

As described in Table 3, according to the present invention, even if the replenishment amount is reduced, the fluctuations in gradation and fog density are greatly reduced, and it can be seen that stable processing can be performed.

Example 2 The procedure of Example 1 was repeated except that the processing steps and the composition of the processing solution were changed as follows.

As a result, as in the case of Example 1, fluctuations in gradation and fog density were extremely small, and stable performance was obtained.

In the above table, the replenishment amount is per 1 m ² of the photosensitive material.

The composition of the processing solution used is described below.

(Bleaching / fixing solution) Common for mother liquor and replenisher (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0
Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700g /) 240.0ml Ammonia water (27%) 6.0ml Add water 1.0 pH 7.2 (Washing solution) Water was passed through a mixed-bed column filled with a cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and an OH type anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / The following treatment was carried out, followed by addition of 20 mg / sodium isocyanurate dichloride and 1.5 g / sodium sulfate.

 The pH of this solution was in the range of 6.5-7.5.

(Stable liquid) Common to mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 pH 5.0-8.0 Example 3 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in a multi-layer manner to prepare a multilayer color photosensitive material 201.

(Composition of photosensitive layer) The numbers corresponding to the respective components are indicated by the same notation as that shown in Example 1.

(Sample 201) First layer; anti-halation layer Black colloidal silver ... silver 0.15 U-1 ... 0.5 U-2 ... 0.2 HBS-3 0.4 gelatin ... 1.5 Second layer intermediate layer C-7 ... 0.10 C -3 ... 0.11 2,5-di-t-octylhydroquinone ... 0.05 HBS-1 ... 0.10 Gelatin ... 1.50 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (5 mol% of silver iodide) , Coefficient of variation on particle size
Emulsion with 17% monodispersity and average particle size of 0.4μ) 0.9 C-12 ... 0.35 C-13 ... 0.37 C-3 ... 0.12 C-10 ... 0.052 HBS-3 ... 0.30 Sensitization Dye I: 4.5 × 10 ^-4; II: 1.4 × 10 ^-5; III: 2.3 × 10 ^-4; IV: 3.0 × 10 ^-5 Gelatin: 1.50 Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, variation coefficient related to grain size)
16% monodisperse emulsion having an average particle size of 1.0 μ) 1.0 sensitizing dye I 3.0 × 10 ^{-4 and} II × 1.0 × 10 ^{-5 and} III × 1.5 × 10 ^{-4 and} IV … 2.0 × 10 ^-5 C-4… 0.078 C-11… 0.020 C-3… 0.025 HBS-1… 0.010 Gelatin… 0.80 Fifth layer: Intermediate layer 2,5-di-t-octylhydroquinone 0.12 HBS-1 0.20 Gelatin 1.0 Sixth layer: First green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, variation coefficient related to grain size)
Emulsion with 17% and an average particle size of 0.4 μ) 0.5 Sensitizing dye V 6.0 × 10 ^-5 VI ・ ・ ・ 2.0 × 10 ^-4 VII ・ ・ ・ 4.0 × 10 ^-4 C-6… 0.27 C -1 ... 0.072 C-7 ... 0.12 C-8 ... 0.010 HBS-1 ... 0.15 Gelatin ... 0.70 Seventh layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (silver iodobromide 7 mol%) An emulsion having a coefficient of variation of 18% and an average particle size of 0.9 μm: sensitizing dye V: 4.0 × 10 ^-5; VI: 1.5 × 10 ^-4; VII: 3.0 × 10 ^-4 C- 6 ... 0.071 C-1 ... 0.021 C-7 ... 0.016 HBS-1 ... 0.10 Gelatin ... 0.91 Eighth layer: Intermediate layer 2,5-di-t-actylhydroquinone ... 0.05 HBS-2 ... 0.10 Gelatin 0.70 Ninth layer: Emulsion layer Silver iodobromide (silver iodide 4 mol%, coefficient of variation with respect to grain size 15%)
Emulsion having an average particle size of 0.4μ) 0.40 Sensitizing dye X 5.0 × 10 ^-4 C-8 0.051 C-14 0.095 HBS-1 0.15 HBS-2 0.15 Gelatin 0.60 Layer 10 : Yellow filter layer Yellow colloidal silver ... 0.85 2,5-di-t-actylhydroquinone ... 0.15 HBS-1 ... 0.20 Gelatin ... 0.80 11th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion ( Silver iodide 4 mol%, coefficient of variation on grain size
(Emulsion having an average particle size of 0.3 μm at 16%) Sensitizing dye VIII: 7.0 × 10 ^-4 Cp-7: 0.80 C-8: 0.050 HBS-2: Amount described in Table 6 Gelatin: 1.5 12th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 8 mol%, variation coefficient related to grain size)
Emulsion having 19% and an average particle size of 0.7 μm) Sensitizing dye VIII: 1.5 × 10 ^-4 C-9: 0.31 HBS-1: 0.12 Gelatin: 0.88 13th layer: intermediate layer U-1: 0.12 U-2: 0.16 HBS-3: 0.12 Gelatin: 0.75 14th layer: protective layer Silver iodobromide emulsion (silver iodide 4 mol%, coefficient of variation with respect to grain size)
0.15 polymethylmethacrylate particles (diameter 1.5μ) 0.15 S-1 ... 0.15 S-2 ... 0.05 Gelatin ... 0.80 Each layer has a surfactant in addition to the above composition. And a gelatin hardener H-1 were added.

(Samples 202 to 206) Cp-7 in the eleventh layer of Sample 201 was replaced with the coupler shown in Table 6 in an equimolar amount, HBS-1 was changed to the amount shown in Table 6, and each raw sample was The amount of gelatin applied was changed to equalize the film quality. The film quality was adjusted by the scratching strength of a raw sample with a 0.1 μ diamond needle and the sweating phenomenon after 7 days at 60 ° C. and 70% relative humidity.

Next, after the sample 201 cut into a 35 mm width was put into a camera and exposed, in processing No. 5-9 described in Table 4,
The processing was performed intermittently by an automatic processor at 10 m / day until the cumulative replenishment of the color developing replenisher reached 16.

In addition, in the same manner as described in Example 1, fluctuations in gradation and fog density were calculated.

Further, at the start of each processing (when each liquid is a new liquid), the liquid circulation amount in the color developing tank is processed at 4 / min and 8 / min.
The change in yellow gradation at 8 / min with respect to the case of / min was evaluated as stirring dependency.

In the above table, the replenishment amount is per 1 m ² of the photosensitive material.

(Washing solution) Common for mother liquor and replenisher Mixing tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water was passed through the bed column to treat the calcium and magnesium ion concentrations to 3 mg / or less, and then 20 mg / sodium dichloride isocyanurate and 130 mg / sodium sulfate were added.

 The pH of this solution is in the range 6.5-7.5.

(Stable liquid) Common to mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 pH 5.0-8.0 As shown in Table 6, the present invention shows excellent effects even when the color development processing is accelerated to high temperatures. Furthermore, according to the present invention, the agitation dependency is reduced, and a process with good stability can be performed.

In particular, when the chelating agents represented by the general formulas (II), (III) and (IV) are used in a color developing solution, the stability can be further improved.

Structures of compounds used in Examples 1 and 3 HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate HBS-3 Tri-n-hexyl phosphate Sensitizing dye

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-55-161239 (JP, A) JP-A-62-135830 (JP, A) JP-A-62-99750 (JP, A) 269149 (JP, A) JP-A-51-53825 (JP, A) JP-A-56-151932 (JP, A) JP-A-62-54258 (JP, A) JP-A-62-206549 (JP, A) JP-A-60-247241 (JP, A) JP-A-61-61160 (JP, A) JP-A-61-189538 (JP, A)

Claims (6)

(57) [Claims] 1. A support comprising a silver halide emulsion layer containing a cyan coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a yellow coupler on a support. One is a lipophilic 2-equivalent yellow coupler represented by the following general formula [I] having an equivalent molecular weight of 450 to 720, and a high boiling point organic solvent is added in a weight ratio to the total amount of the yellow coupler contained in the emulsion layer. The silver halide color photographic light-sensitive material containing 0.5 or less 1m
^{2. A} method for processing a silver halide color photographic light-sensitive material, wherein a color developer is replenished by replenishing a replenisher of a color developing solution of 200 ml or more and 500 ml or less per ² parts. General formula [I] In the general formula [I], R ^I and R ^II represent groups (including atoms) substitutable on a benzene ring, R ^III represents a hydrogen atom, a halogen atom or an aliphatic oxy group, and m represents 0 or 1 to 5 X represents an integer, n represents an integer of 0 or 1 to 4, and X represents a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (R ^I ) _m may be the same or different, and when n is plural, (R ^III ) _n may be the same or different. Also R ^I , R
^II , R ^III or X may be a divalent to tetravalent linking group to form a dimer or tetramer of a yellow coupler represented by the general formula [I]. 2. The method for processing a silver halide color photographic material according to claim 1, wherein the replenisher of the color developing solution is substantially free of bromide. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein after color development, processing is performed with a processing solution having a pH of 6 or more. 4. The color developing solution according to any one of formulas (II), (III) and (I)
2. A method for processing a silver halide color photographic material according to claim 1, which contains at least one chelating agent represented by V). General formula (III) General formula (IV) In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represents a hydrogen atom or an alkali metal atom. 5. A process subsequent to the color developing process is a process having a fixing ability, and a further subsequent process is a washing or stabilizing process for replenishing 3 to 50 times the processing liquid brought in from the preceding process. 3. The method for processing a silver halide color photographic light-sensitive material according to item 1. 6. The processing method according to claim 5, wherein the overflow of the washing or stabilizing step flows into the step having a fixing ability.