JPH077195B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a transparent support, and more specifically, it is fogged even after continuous processing for a long period of time. The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a transparent support which is capable of maintaining stable processing characteristics without generation of blemishes.

BACKGROUND OF THE INVENTION The processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, a rinse treatment, a stabilizing treatment, or a water washing alternative stabilizing treatment is added as an additional treatment step.

In color development exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as inhibitors contained in the silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photographic light-sensitive material as soluble silver salts with a fixing agent. There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

Usually, a sulfite salt or a water-soluble salt of sulfite salt and hydroxylamine is added to the color developing solution in order to increase its storage stability. Among them, as in the former case, fogging is remarkable in the case of using sulfite alone, so by using a combination of sulfite salt and water-soluble salt of hydroxylamine as in the latter case, the storage stability of the developer is remarkably increased. In addition, the generation of fogging due to the aged developer is reduced.

However, hydroxylamine has the following drawbacks and disadvantages.

First, it was reported that hydroxylamine is harmful to the human body [eg PGStecher, “The Merck
Index An Encyclopedia of Chemical and Drugs "8th.Ed. (195
3 years)].

Secondly, even in the Poisonous and Deleterious Substances Control Law, in order to handle and sell hydroxylamine salts, it is necessary to register a general sales business of poisonous and deleterious substances and to set up a person in charge of handling them, which is extremely inconvenient to handle. Is.

Thirdly, hydroxylamine is a kind of black-and-white developer and has silver developability with respect to silver halide. Therefore, the utilization efficiency of silver halide in the silver halide color photographic light-sensitive material is poor, and it is necessary to use more silver halide or coupler in the light-sensitive material in order to obtain a desired dye concentration, which is economical. Is extremely detrimental to.

Fourthly, hydroxylamine has a drawback that it decomposes when heavy metal ions (for example, iron ions or copper ions) are mixed in the color developing solution and becomes ammonia, causing fogging on the color light-sensitive material. ing. From the viewpoint of economical efficiency and pollution, color developers tend to be low in replenishment in recent years, and the grade of raw materials such as potassium carbonate is being reduced for the purpose of cost reduction. The amount of the heavy metal ions accumulated in the developing solution is increasing more and more. Therefore, the fourth problem "occurrence of fogging" is caused by the decomposition of hydroxylamine.
Is becoming more difficult.

Therefore, many preservatives replacing hydroxylamine having the above first to fourth problems have been proposed in recent years, for example, 2-anilinoethanol (see US Pat. No. 3,823,017).
And dihydroxyalkene (see US Pat. No. 3,615,503) have been proposed. However, these 2-
Both anilinoethanol and dihydroxyalkene have inadequate compound stability, and have a very small effect of preventing fogging.

On the other hand, in recent years, the image size of the film has been reduced in order to reduce the size of the camera and improve portability, but it is well known that the print image deteriorates if this is done. That is, when the screen size of the color photographic light-sensitive material is reduced, the enlargement ratio is increased to produce a print of the same size, and thus the graininess and sharpness of the printed image are inferior. Therefore, it is necessary to improve the graininess, resolution and sharpness of the film in order to obtain a good print even if the camera is downsized.

DIR coupler (Development Inh
ibitor Releasing Coupler, also known as development inhibitor-releasing coupler, is disclosed in US Pat. No. 3,227,554 and Pho
to, Sci. Eng., 13 , 74, 214 (1969) and the like.

However, when these DIR couplers are used, the development inhibitor is released to the highest density part and is adsorbed on the surface of developed silver, and it is difficult for the bleaching agent to act on the developed silver in the subsequent silver bleaching step, resulting in desilvering. It has the drawback that defects are likely to occur.

In particular, in recent years, bleaching solutions and bleach-fixing solutions have been reduced in replenishment from the viewpoints of their economic efficiency and pollution prevention, and color developing solution components brought into the photosensitive material by adhering to these processing solutions having bleaching ability. The accumulated amount of
Poor desilvering is becoming more and more prominent.

[Object of the Invention] Accordingly, the present invention clarifies a preservative that replaces hydroxylamine having the above-mentioned first to fourth drawbacks or disadvantages, and eliminates the deprotection that occurs when a DIR coupler is used as an image improving technique. It is an object of the present invention to clarify a processing method of a silver halide color photographic light-sensitive material which can solve the problem of silver failure.

[Means for Solving Problems] A method of processing a silver halide color photographic light-sensitive material of the present invention which achieves the above object is to process a silver halide color photographic light-sensitive material having a transparent support with a color developer. In the method for processing a silver halide color photographic light-sensitive material, the DI is represented by the following general formula [I] or (D-1).
At least one of the silver halide emulsion layers contains an R compound and tabular silver halide grains containing 0.5 mol% or more of silver iodide, and the color developer is represented by the following general formula [A]. It is characterized by containing a compound.

General formula [A] (In the formula, R and R'are each a hydrogen atom and a carbon number of 1 to 5
Represents an unsubstituted alkyl group or a substituted alkyl group. However, R and R'are not hydrogen atoms at the same time, and R and R'may be bonded to each other to form a nitrogen-containing heterocycle together with> N-. General formula [I] A ₁ -Z ₁ (In the formula, A ₁ is a coupler component capable of coupling with an oxidized product of a p-phenylenediamine color developing agent, and Z ₁ is a reaction with a p-phenylenediamine color developing agent. To leave,
The components that suppress the development of silver halide are shown below. ) General formula (D-1) AY) _m (In the formula, A represents a coupling component, m represents 1 or 2, Y couple | bonds with the coupling position of the coupling component A, p,
-Represents a group that is released by a reaction with an oxidant of a phenylenediamine color developing agent and becomes a development inhibitor having a large diffusibility or a compound capable of releasing a development inhibitor. ) [Operation of the Invention] As a result of intensive studies conducted by the present inventors in order to achieve the above object, the present inventors have found that alkylhydroxylamine is extremely useful as a preservative in place of hydroxylamine having the first to fourth drawbacks or disadvantages. It was found to be effective. And while conducting research on the alkylhydroxylamine,
Compared with conventional so-called hydroxylamine, alkylhydroxylamine is more likely to remain in the light-sensitive material, and this residual alkylhydroxylamine also improves the deterioration of desilvering performance due to the DIR coupler, and at the same time produces tabular halogen as silver halide. The inventors of the present invention have found that the effect is great in the processing of a light-sensitive material using silver halide, and have reached the present invention.

The present invention will be described in detail below.

First, the general formula [A] will be described.

R and R'are not simultaneously hydrogen atoms. Each represents an alkyl group or a hydrogen atom, and the alkyl groups represented by R and R'may be the same or different and each has 1 carbon atom.
Alkyl groups of 5 to 5 (eg methyl group, ethyl group, n-propyl group, iso-propyl group, butyl group, etc.) are preferable, and in the present invention, alkyl groups having 1 to 3 carbon atoms are particularly preferable. The alkyl groups of R and R'include those having a substituent, and examples of the substituent include an amino group, an alkoxy group (for example, a methoxy group, etc.), a sulfonic acid group, a carboxylic acid group, a hydroxyl group and the like. , For example US patents
The hydroxylamines described in 3,287,125, 3,293,034, 3,287,124 and the like can be mentioned.

R and R'may be combined to form a nitrogen-containing heterocycle with> N-, for example, a heterocycle such as piperidine or morpholine.

The preferred specific exemplary compounds represented by the general formula [A] are shown below.

[Exemplified compound] The compound of the present invention represented by the general formula [A] may be used as a salt of an organic acid and an inorganic acid, for example, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphoric acid. It may be used in the form of salt such as salt or acetate.

Among the compounds represented by the above general formula [A], (I-1), (I-2), (I-8), (I-10) and (I-20)
Are preferably used from the viewpoint of the effect of the object of the present invention.

The concentration of the compound of the present invention represented by the general formula [A] in the color developer is usually the same as that of hydroxylamine used as a preservative, for example, 0.1 g / l to 50 g / l is preferable. , More preferably 0.5 g / l to 30 g / l, particularly preferably 1 g / l to 20 g / l.

The method of incorporating the compound of the present invention represented by the general formula [A] into the color developing solution is arbitrary, and it may be added directly, or may be added to the color developing replenisher, or the pre-bath May be provided by means of a light-sensitive material from this prebath, or the compound of the present invention contained in the backing layer of the light-sensitive material may be eluted and accumulated.

Besides the above, details of the color developing solution used in the present invention will be described later.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor or a development inhibitor precursor, and is a non-diffusible DIR compound.
It may be a compound or a diffusible DIR compound.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. , U.S. Patent 3,227,5
54, 4,095,984, 4,149,886, etc.

The above-mentioned DIR coupler has a property that, when it undergoes a coupling reaction with an oxidized product of a color developing agent, the coupler nucleus forms a dye, while releasing a development inhibitor. Further, in the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529.
No. 54-13333, No. 55-161237, etc., a compound that releases a development inhibitor but does not form a dye when subjected to a coupling reaction with an oxidant of a color developing agent is described. .

Furthermore, the mother nucleus forms a dye or a colorless compound when reacted with an oxidant of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234. On the other hand, the present invention also includes a so-called timing DIR compound in which the released timing group is a compound that releases the development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction.

Further, the timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye when it reacts with the oxidized product of the color developing agent described in JP-A-58-160954 and JP-A-58-162949. It also includes a bound timing DIR compound.

According to the present invention, the DIR compound is represented by the following general formula [I] and / or
Alternatively, the most preferred DIR compound can be represented by (D-1), and the most preferred DIR compound is a compound represented by the following general formula (D-1) having a diffusivity of 0.34 or more.
Is a compound represented by.

In formula (I) A ₁ -Z ₁ , A ₁ is a coupler component (compound) capable of coupling with an oxidant of a p-phenylenediamine color developing agent,
For example, acylacetanilides, closed ketomethylene compounds such as acyl acetates, pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles, indazolones, phenols, dye-forming couplers such as naphthols and acetophenones, indanones, Coupling components such as oxazolones that do not substantially form pigments.

Z ₁ in the above formula is a component (compound) which is released by the reaction with a p-phenylenediamine color developing agent and suppresses the development of silver halide, and preferred compounds are benztriazole and 3-octylthio- There are heterocyclic compounds such as 1,2,4-triazole and heterocyclic mercapto compounds (the heterocyclic mercapto group includes i-phenyltetrazolylthio group).

Examples of the heterocyclic group include a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, and a triazolyl group. Specifically, a 1-phenyltetrazolyl group,
1-ethyltetrazolyl group, 1- (4-hydroxyphenyl)
Tetrazolyl group, 1,3,4-thiazolyl group, 5-methyl-1,3,
There are 4-oxadiazolyl group, benzthiazolyl group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group and the like.

In the above general formula [I], Z ₁ is bonded to the active site of A ₁ .

Hereinafter, typical specific examples of the DIR compound represented by the general formula [I] will be described, but the present invention is not limited thereto.

[Exemplified compound]

In the present invention, the diffusible DIR compound is a diffusivity of a compound which is released by the reaction with an oxidized product of a color developing agent and which releases a development inhibitor or a development inhibitor and has a diffusivity of 0.34 or more according to the evaluation method described below. It is preferable that the diffusivity is 0.40 or more. The diffusivity is evaluated by the following method.

Photosensitive material samples (I) and (II) having a layer having the following composition are prepared on a transparent support.

Sample (I): Sample having edge-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to edge sensitivity (silver iodide 6 mol%, average particle size 0.48 μm) and the following coupler per 1 mol of silver, 0.
A gelatin coating solution containing 07 moles was coated with a silver amount of 1.1 g / m ² ,
It was coated so that the amount of gelatin applied would be 3.0 g / m ² , and silver iodobromide (2 mol% silver iodide, average grain size 0.08 μm) that had not been chemically or spectrally sensitized as a protective layer thereon. ) Containing a gelatin coating solution with a silver amount of 0.1 g / m ² and a gelatin coating amount of
Apply so that it becomes 0.8 g / m ² .

Sample (II): Silver iodobromide removed from the protective layer of Sample (I).

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

Samples (I) and (II) are exposed to white with a wedge and then processed according to the following processing method. Sample (II) for developer
The amount of each development inhibitor which suppresses the sensitivity to 60% (-Δlog E = 0.22 in logarithmic display) and the one to which no development inhibitor is added are used.

Treatment process (38 ℃) Color development 2 minutes 40 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment liquid used in each processing step is as follows. Is the street.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1 and adjust to pH 10.06 with 50% sulfuric acid and potassium hydroxide.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1 and adjust the pH to 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

The sensitivity of the sample (I) when the development inhibitor is not added is So, the sensitivity of the sample (II) is So ′, the sensitivity of the sample (I) when the development inhibitor is added is S _I, and the sensitivity of the sample (II sensitivity) When S _II, expressed as reduced sensitivity △ S = So-S decrease the sensitivity of _I samples (II) △ So = So'- S II diffusible = △ S / △ So samples (I) .

However, all sensitivities are the logarithm (-log E) of the reciprocal of the exposure amount at the density point of fog density +0.3.

The diffusivity of several development inhibitors determined by this method is illustrated in the table below.

The diffusible DIR compound can be selected from compounds represented by the following general formulas, for example.

General formula (D-1) AY) m In formula, A represents a coupling component, m represents 1 or 2, Y couple | bonds with the coupling position of the coupling component A, and p-
It represents a group which is released by a reaction with an oxidant of a phenylenediamine color developing agent and becomes a development inhibitor having a large diffusibility or a compound capable of releasing the development inhibitor.

It suffices that A has a property of undergoing a coupling reaction with an oxidized product of a p-phenylenediamine color developing agent, and it is not always necessary to form a dye by coupling.

In the general formula (D-1) of the diffusible DIR compound, Y is preferably represented by the following general formulas (D-2) to (D-19).

General formula (D-2) General formula (D-3) General formula (D-4) General formula (D-5) General formula (D-6) General formula (D-7) General formula (D-8) General formula (D-9) In the general formulas (D-2) to (D-7), Rd ₁ represents a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group,
Halogen atom, alkoxycarbonyl group, thiazolidinylideneamino group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group Represents a group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, heterocyclic group, cyano group, alkylsulfonyl group or aryloxycarbonylamino group. General formula (D-2)-(D-5)
And (D-7), n represents 0, 1 or 2,
When n is 2, each Rd ₁ may be the same or different, and n R
The total number of carbon atoms contained in d ₁ is 0 to 10. The number of carbon atoms contained in Rd ₁ in the general formula (D-6) is 0 to 15.

X in the general formula (D-6) represents an oxygen atom, a sulfur atom or a selenium atom.

In the general formula (D-8), Rd ₂ represents an alkyl group, an aryl group or a heterocyclic group.

In formula (D-9), Rd ₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and Rd ₄ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, It represents an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a hetrocyclic group, an alkylthio group or an amino group.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents an alkyl group, the alkyl group includes those having a substituent and may be substituted or unsubstituted, linear or branched, or cyclic. It may be an alkyl group. As a substituent, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group,
Examples thereof include an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an amino group, an alkylthio group and an arylthio group.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents an aryl group, the aryl group includes those having a substituent. As the substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group. Group, acylamino group, cyano group or ureido group.

When Rd ₁ , Rd ₂ , Rd ₃ or Rd ₄ represents a heterocyclic group, this heterocyclic group includes those having a substituent, and includes a 5-membered or 6-membered hetero atom including a nitrogen atom, an oxygen atom and a sulfur atom. A monocyclic or condensed ring of a member ring is preferable, for example, pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group,
It is selected from a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group and the like, and a group obtained by substituting these groups with the substituents listed for the aryl group.

In the general formulas (D-6) and (D-8), the number of carbon atoms contained in Rd ₂ is 0 to 15.

In the general formula (D-9), the total number of carbon atoms contained in Rd ₃ and Rd ₄ is 0 to 15.

General formula (D-10) -TIME-INHIBIT In the formula, the TIME group is a group which is bonded to the coupling position of A and can be cleaved by the reaction with the color developing agent, and after cleaving from the coupler, the INHIBIT group is appropriately suppressed. Is a group that can be released. The INHIBIT group is a group that serves as a development inhibitor (for example, the groups represented by the general formulas (D-2) to (D-9)).

In the general formula (D-10), the -TIME-INHIBIT group is preferably represented by the following general formulas (D-11) to (D-19).

General formula (D-11) General formula (D-12) General formula (D-13) General formula (D-14) General formula (D-15) General formula (D-16) General formula (D-17) General formula (D-18) General formula (D-19) In formulas (D-11) to (D-15) and (D-18), Rd ₅ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, or acylamino. Represents a group, a ureido group, a cyano group, a nitro group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, an alkanesulfonyl group, and is represented by the general formula (D-11) to (D- 13), (D-15), (D-1
In 8), Rd _{5 s} may combine with each other to form a condensed ring, and in the general formulas (D-11), (D-14), (D-15) and (D-19), Rd ₆ is Represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, a heterocyclic group or an aryl group, and in the general formulas (D-16) and (D-17), Rd ₇ represents a hydrogen atom, an alkyl group, an alkenyl group or an aralkyl group. , A cycloalkyl group, a heterocyclic group or an aryl group, and Rd ₈ and Rd ₉ in the general formula (D-19) each represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms), K in the formulas (D-11) and (D-15) to (D-18)
Represents an integer of 0, 1 or 2, and is represented by general formulas (D-11) to (D-13), (D-15), (D-1)
L in 8) represents an integer of 1 to 4, m in the general formula (D-16) represents an integer of 1 or 2, and when m is 2, each Rd ₇ may be the same or different, and (D- N in 19) represents an integer of 2 to 4, and n Rd
₈ and Rd ₉ may be the same or different, and B in the general formulas (D-16) to (D-18) is an oxygen atom or (R ₆ represents the same meaning as previously defined), and in the general formula (D-16) Represents a single bond or a double bond, m is 2 in the case of a single bond and m in the case of a double bond.
Is 1 and the INHIBIT group is represented by the general formula (D-2) to (D-
Except for the number of carbon atoms, it has the same meaning as the general formula defined in 9).

The number of carbon atoms contained in Rd ₁ in one molecule of the general formulas (D-2) to (D-7) is 0 to 32 in total, and the INHIBIT group is contained in Rd ₂ of the general formula (D-8). The number of carbon atoms is 1 to 32, and Rd ₃ and Rd ₄ in the general formula (D-9) are
The total number of carbon atoms contained in is 0 to 32.

When Rd ₅ , Rd ₆ and Rd ₇ represent an alkyl group, they include those having a substituent and may be either linear or cyclic. Examples of the substituent include the substituents enumerated when Rd _{1 to} Rd ₄ are alkyl groups.

When Rd ₅ , Rd ₆ and Rd ₇ represent an aryl group, the aryl group includes those having a substituent, and as the substituent, Rd ₁ to Rd ₄
And the substituents enumerated when is an aryl group.

Among the coupling components represented by A in the general formula (D-1), as the yellow color image forming coupler residue, a pivaloyl acetanilide type, a benzoyl acetanilide type, a malon diester type, a malon diamide type, a dibenzoyl methane type, Benzothiazolyl acetamide type, malon ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolyl acetamide type, or benzimidazolyl acetate type coupler residue Group, a coupler residue derived from a heterocyclic-substituted acetamide or a heterocyclic-substituted acetate contained in U.S. Pat.
770,446, British patent 1,459,171, West German patent (OLS) 2,5
03,009, coupler residues derived from acylacetamide described in JP-A-50-139738 or Research Disclosure 15737, or heterocyclic coupler residues described in US Pat. No. 4,046,574.

Among the coupling components represented by A, the magenta color image-forming coupler residue is a 5-oxo-2-pyrazoline nucleus,
A coupler residue having a pyrazolo- [1,5-a] benzimidazole nucleus or a cyanoacetophenone type coupler residue is preferred.

Among the coupling components represented by A, the cyan image forming coupler residue is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, and an indazolone or pyrazolotriazole coupler residue.

Further, the effect as a DIR coupler is the same even when the coupler is coupled with the oxidized product of the developing agent to release the development inhibitor or the compound capable of releasing the development agent, and substantially no image dye is formed. Examples of this type of coupling component represented by A include U.S. Pat. Nos. 4,052,213 and 4,088,491.
No. 3,632,345, No. 3,958,993, No. 3,961,959, etc., and the like.

The preferred diffusible DIR compounds used in the present invention include, but are not limited to, the following compounds.

The DIR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and / or a non-light-sensitive photographic constituent layer, but is preferably added to a light-sensitive silver halide emulsion layer.

Two or more kinds of the DIR compound of the present invention may be contained in the same layer.
The same DIR compound may be contained in two or more different layers.

To incorporate these DIR compounds into the silver halide emulsion according to the present invention or other photographic constituent layer coating solution,
When the DIR compound is alkali-soluble, it may be added as an alkaline solution, and when it is oil-soluble,
For example, U.S. Patent Nos. 2,322,027, 2,801,170, and
No. 2,801,171, No. 2,272,191 and No. 2,304,940, the DIR compound is dissolved in a high-boiling solvent according to the method described in the specification by dissolving a low-boiling solvent, if necessary, and dispersed in fine particles to be halogenated. It is preferably added to the silver emulsion. At this time, two or more kinds of DIR compounds may be mixed and used if necessary. Furthermore, in detail, the preferred method of adding a DIR compound in the present invention is to use one or more DIR compounds as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons. And the like, especially di-n-butyl phthalate, tricresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N, N-di-ethyl-caprylamide Butyl, N, N-diethyllaurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di High boiling point solvent such as -o-chlorophenyl phosphate or fluoroparaffin, and / or vinegar Methyl, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,
Diethylene glycol monoacetate, nitromethane,
Soluble in a low boiling point solvent such as carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane and methyl ethyl ketone, and an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or sorbitan sesquiolein. Acid ester and a nonionic surfactant such as sorbitan monolaurate and / or an aqueous solution containing a hydrophilic binder such as gelatin and the like, and a high-speed rotating mixer,
It is emulsified and dispersed by a colloid mill or an ultrasonic disperser and added to the silver halide emulsion.

In addition, the DIR compound may be dispersed using a latex dispersion method. The latex dispersion method and its effect are described in JP-A-49-74538, JP-A-51-59943 and JP-A-54-32552, and Research Disclosure, August 1976, No. 148.
50, p. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide,
Homopolymers, copolymers and terpolymers of monomers such as N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like.

The above-mentioned DIR compounds are described in U.S. Patents 3,227,554 and 3,615,50.
No. 6, No. 3,617,291, No. 3,632,345, No. 3,928,041,
3,933,500, 3,938,996, 3,958,993, 3,9
61,959, 4,046,574, 4,052,213, 4,063,95
0, 4,095,984, 4,149,886, 4,234,678,
British Patent Nos. 2,072,363 and 2,070,266, Research Disclosure 21228 (1981), JP-A-50-81144
No. 50, No. 81-145145, No. 51-13239, No. 51-64927,
51-104825, 51-105819, 52-65433, 5
2-82423, 52-117627, 52-130327, 52-
No. 154631, No. 53-7232, No. 53-9116, No. 53-29717
No. 53-70821, No. 53-103472, No. 53-110529
No. 53-135333, No. 53-143223, No. 54-13333
No. 54, No. 54-13838, No. 54-114241, No. 57-35858,
54-145135, 55-161237, 56-114946,
57-154234, 57-56837 and Japanese Patent Application No. 57-44831,
It can be synthesized by the method described in JP-A-57-45809.

The DIR compound of the present invention can be added to the light-sensitive silver halide emulsion layer and / or the non-light-sensitive photographic constituent layer as described above, but it is preferably contained in at least one of the silver halide emulsion layers. Is. For example, when it is applied to an ordinary multilayer color photographic light-sensitive material having a blue light-sensitive silver halide emulsion, a green light-sensitive silver halide emulsion and a red light-sensitive silver halide emulsion, it is contained in one or more layers of these. You can do it.

Next, the silver halide color photographic light-sensitive material to which the processing method of the present invention is applied will be described in detail.

The silver halide in the silver halide emulsion layer used in the present invention preferably contains at least 0.5 mol% of silver iodide grains, but the sensitivity and photographic characteristics of the color light-sensitive material and the color developing performance of the present invention are maximized. In view of photographic characteristics and color developability, silver iodide content is preferably 2 to 15 mol%, particularly preferably 3 to 8 mol%.

The tabular silver halide grains preferably used in the present invention will be described below.

The tabular silver halide grains of the present invention preferably have a grain size of 5 times or more the grain thickness. The tabular silver halide grains are described in JP-A Nos. 58-113930, 58-113934 and 58-127921.
No. 58-108532 and the like, and in the present invention, the particle size is 3 times or more of the particle thickness in view of effects on color stain and image quality. It is preferably 3 to 100 times, particularly preferably 5 to 30 times. Further, the particle size is preferably 0.3 μm or more, and the particle size of 0.5 to 6 μm is particularly preferably used. These tabular silver halide grains more preferably exhibit the effects of the object of the present invention when they are contained in at least 50% by weight of at least one silver halide emulsion, and almost all of them are the tabular silver halide grains described above. When
Especially, a particularly preferable effect is exhibited.

It is particularly useful when the tabular silver halide grain of the present invention is a core-shell grain.

In general, tabular silver halide grains are tabular having two parallel planes, so that the "thickness" in the present invention is represented by the distance between two parallel planes constituting the tabular silver halide grain. .

The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide, and particularly preferably silver iodobromide having a silver iodide content of 3 to 10 mol%.

Next, the method for producing the tabular silver halide grains of the present invention will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, in an atmosphere with a relatively high pAg value of pBr 1.3 or less, tabular silver halide grains form a seed crystal in which 40% or more by weight exists, and silver and a halogen solution are simultaneously treated while maintaining a similar pBr value. It is obtained by growing seed crystals while adding.

In this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and controlling the addition rate of silver salt and halide used during grain growth.

During the production of the tabular silver halide grains of the present invention, a silver halide solvent is optionally used to control the grain size, grain shape (diameter / thickness ratio, etc.), grain size distribution, grain growth rate. You can control. The amount of the silver halide solvent used is preferably 1 × 10 ^{−3 to} 1.0% by weight of the reaction solution, and particularly preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ % by weight.

For example, the growth rate can be increased by monodispersing the silver halide grain size distribution with an increase in the amount of silver halide solvent used. On the other hand, there is also a tendency that the thickness of silver halide grains increases with the amount of silver halide solvent used.

Examples of the silver halide solvent used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Patent Nos. 3,271,157 and 3,790,387
Issue No. 3,574,628, etc. can be referred to.

When the tabular silver halide grains of the present invention are produced, the addition rate, the addition amount, and the addition concentration of the silver salt solution (for example, AgNO ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution), which are added to accelerate the grain growth, are set. A method of increasing the temperature is preferably used.

Regarding these methods, for example, British Patent 1,335,925,
U.S. Patents 3,672,900, 3,650,757, 4,242,445
Reference can be made to the descriptions in JP-A Nos. 55-142329 and 55-158124.

The tabular silver halide grain of the present invention can be chemically sensitized if necessary. Regarding the chemical sensitization method, a general sensitization method can be referred to, but from the viewpoint of silver saving, the tabular silver halide grain of the present invention is preferably gold sensitized or sulfur sensitized, or a combination thereof.

In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular silver halide grains are present in an amount of 40% or more, and particularly 60% or more, by weight based on all the silver halide grains in the layer.

Thickness of layer containing tabular silver halide grains is 0.5 μm
˜5.0 μm, particularly preferably 1.0 μm to 3.0 μm.

Other constitutions of the layer containing the tabular silver halide grains of the present invention, for example, binder, curing agent, antifoggant, stabilizer of silver halide, surfactant, spectral sensitizing dye, dye, ultraviolet absorber There are no particular restrictions on, etc., for example,
Reference can be made to the description in Research Disclosure 176, 22-28 (December 1978).

Next, the constitution of the silver halide emulsion layer (hereinafter referred to as the upper silver halide emulsion layer) existing outside (on the surface side) of the layer containing tabular silver halide grains of the present invention will be described.

The silver halide grains used in the upper silver halide emulsion layer are preferably the high-sensitivity silver halide grains used in ordinary direct X-ray films.

The silver halide grains preferably have a spherical shape, a polyhedral shape, or a mixture of two or more thereof.
In particular, it is preferable that spherical particles and / or polyhedral particles having a diameter / thickness ratio of 5 or less account for 60% or more (weight ratio) of the whole.

The average particle size is preferably 0.5 μm to 3 μm, and if necessary, it can be grown using a solvent such as ammonia, thioether, thiourea or the like.

The silver halide grains are sensitized by a gold sensitization method, a sensitization method with another metal, a reduction sensitization method, a sulfur sensitization method, or a sensitization method by a combination of two or more thereof. Is preferred.

The other constitution of the upper emulsion layer is not particularly limited as in the layer containing tabular silver halide grains.
You can refer to the description in arch Disclosure Volume 176.

The silver halide color photographic light-sensitive material to which the processing of the present invention is applied is not limited to the above, and may contain tabular silver halide grains as shown below.

For example, in JP-A-58-113930, the aspect ratio of the upper layer is
A multilayer color photographic light-sensitive material having a two-layered dye-forming unit having an emulsion amount containing tabular silver halide grains of 8: 1 or more is disclosed in JP-A-58-113934, which is a green-sensitive layer and a red-sensitive layer. And a multilayer color photographic light-sensitive material using a silver iodobromide or silver bromide emulsion of tabular silver halide grains having an aspect ratio of 8: 1 or more, and in JP-A-58-113927, the central region is a circular region. A multilayer color photographic light-sensitive material having tabular silver halide grains having a silver iodide content lower than that of 8: 1 and an aspect ratio of 3: 1 is further disclosed in JP-A-59-55426. The silver halide photographic light-sensitive material applicable to color containing the above tabular silver halide grains and a specific sensitizing dye is further disclosed in Japanese Patent Application No. 60-111696 and has an aspect ratio of 3: 1 or more. And a silver halide color containing tabular silver halide grains mainly composed of (111) faces. -A photographic light-sensitive material is disclosed, and the processing method of the present invention can be applied to these silver halide color photographic light-sensitive materials.

It is also preferable to add epitaxy-bonded silver halide grains described in JP-A-53-103725 to the emulsion of the present invention.

The silver halide grains particularly preferably used in the present invention are
It is substantially monodisperse and may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Since the particle size distribution of the monodisperse emulsion is almost normal, the standard deviation can be easily obtained. The relational expression If the breadth of distribution (%) is defined by
Those having a monodispersity of 20% or less are preferable, and more preferably 10% or less.

In the present invention, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow them to a predetermined size. When growing silver halide grains, control the pH, pAg, etc. in the reaction kettle,
For example, as described in JP-A-54-48521, it is preferable to successively and simultaneously inject and mix silver ions and halide ions in an amount corresponding to the growth rate of silver halide grains.

The silver halide grains according to the present invention are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc. or ruthenium, palladium, platinum, rhodium, iridium Water-soluble salt sensitizers such as ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these are used as sensitizers or antifoggants depending on the amount). Etc.) or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are used in combination, It may be chemically sensitized by using a gold sensitizer and a selenium sensitizer together.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one kind of nitrogen-containing heteroaryl having a hydroxytetrazaindene and a mercapto group. You may make it contain at least 1 sort (s) of a ring compound.

The silver halide used in the present invention contains a sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol per mol of the silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. Then, it may be optically sensitized. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used.

The red-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer according to the present invention can each react with a coupler, that is, an oxidant of a color developing agent to form a dye. A compound can be included.

The yellow coupler which can be used in the present invention includes a closed ketomethylene compound, an active point-o-aryl substituted coupler and an active point-o so-called 2-equivalent type coupler.
-Acyl-substituted coupler, active-point hydantoin compound-substituted coupler, active-point urazole compound-substituted coupler, active-point succinimide compound-substituted coupler, active-point fluorine-substituted coupler, active-point chlorine or bromine-substituted coupler, active-point-o-sulfonyl-substituted coupler Etc. can be used as an effective yellow coupler. Specific examples of usable yellow couplers include U.S. Pat. No. 2,875,057.
Issue, Issue 3,265,506, Issue 3,408,194, Issue 3,551,155,
3,582,322, 3,725,072, 3,891,445, West German Patent 1,547,868, West German Published Application 2,219,917, 2,261,
No. 361, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 5
1-10783, JP-A-47-26133, 48-73147, 51
-102636, 50-50634, 50-123342, 50-13
0442, 51-21827, 50-87650, 52-82424
No. 52-115219, No. 58-95346 and the like.

Examples of magenta couplers that can be used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers that can be used in combination include U.S. Patents 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,476,
3,419,391, 3,519,429, 3,558,319, 3,5
82,322, 3,615,506, 3,834,908, 3,891,44
5, West German patent 1,810,464, West German patent application (OLS) 2,40
No. 8,665, No. 2,417,945, No. 2,418,959, No. 2,424,467
No. 4, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51-20826, No. 52-589
No. 22, No. 49-129538, No. 49-74027, No. 50-159336
No. 52, No. 42121, No. 49-74028, No. 50-60233,
Examples thereof include those described in JP-A-51-26541, JP-A-53-55122 and Japanese Patent Application No. 55-110943.

The silver halide color photographic light-sensitive material processed according to the present invention preferably contains a phenol type cyan coupler having a ureido group in its red-sensitive silver halide emulsion layer, and the coupler is represented by the following general formula [IV] or general The compound represented by the formula [V] is preferable.

General formula (IV) General formula [V] (In the formula, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y represents In a group represented by (wherein R ₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₃ is .R ₂ represents a group represented by a hydrogen atom or R ₂
And R ₃ may be the same or different and are bonded to each other to form 5
A 6-membered heterocycle may be formed. ) And Z each represent a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine type color developing agent. ) Hereinafter, the general formula [IV] and the general formula [V] will be described in detail.

In the above general formula [IV] and general formula [V], Y is Is a group represented by. Here, R ₁ and R ₂ are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, t-butyl, dodecyl groups, etc.), an alkenyl group, preferably an alkenyl having 2 to 20 carbon atoms. Group (allyl group, heptadecenyl group, etc.), cycloalkyl group, preferably 5- to 7-membered ring (eg, cyclohexyl, etc.), aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably It represents a 5- to 6-membered ring group (for example, a furyl group, a thienyl group, a benzothiazolyl group, etc.) containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms. R ₃ represents a hydrogen atom or a group represented by R ₂ . R ₂ and
It may combine with R ₃ to form a 5- or 6-membered heterocycle. It should be noted that any substituent can be introduced into R ₁ and R ₂ , for example, an alkyl group having 1 to 10 carbon atoms (for example, methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.). , Aryl groups (eg, phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (eg, methanesulfonamide,
Butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbamoyl group (eg, dimethyl) Carbamoyl, phenylcarbamoyl etc.), oxycarbonyl group (eg ethoxycarbonyl, phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl etc.), heterocycle (eg pyridyl group, pyrazolyl group etc.), alkoxy group, aryloxy group, acyloxy A group etc. can be mentioned.

In the general formulas [IV] and [V], R ₁ imparts diffusion resistance to the cyan coupler represented by the general formulas [IV] and [V] and the cyan dye formed from the cyan coupler. Represents a ballast group required for. Preferably, an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group,
It is a cycloalkyl group or a heterocyclic group. For example, a linear or branched alkyl group (eg t-butyl, n-octyl,
t-octyl, n-dodecyl and the like) and 5- or 6-membered heterocyclic groups.

In the general formulas [IV] and [V], Z represents a hydrogen atom or a group capable of splitting off during the coupling reaction with the oxidation product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent. For example, halogen atom (eg chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group, alkylthio group, arylthio group, heterocycle Examples thereof include a thio group and a sulfonamide group. More specific examples include U.S. Pat. No. 3,741,563, JP-A-47-37425, and JP-B-48-36.
894, JP-A-50-10135, 50-117422, 50-13
0441, 51-108841, 50120343, 52-18315
No. 53-105226, No. 54-14736, No. 54-48237,
55-32071, 55-65957, 56-1938, 56-
12643, 56-27147, 59-146050, 59-1669
No. 56, No. 60-24547, No. 60-35731, No. 60-37557, etc. can be mentioned.

In the present invention, a cyan coupler represented by the general formula [IV] is preferable.

General formula (IV) In the general formula [IV], R ₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). Examples of the substituent in the case where the aryl group has a substituent, -SO ₂ R _5, a halogen atom (fluorine, chlorine _{bromine), - CF 3, -NO 2} , -C
N, -COR ₅ , -COOR ₅ , -SO ₂ OR ₅ , At least one substituent selected from is included.

Here, R ₅ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl groups, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (allyl). Group, heptadecenyl group, etc.), a cycloalkyl group, preferably a 5- to 7-membered ring (eg cyclohexyl etc.), an aryl group (eg phenyl group, tolyl group, naphthyl group etc.), and R ₆ is a hydrogen atom or R _Five
Is a group represented by.

A preferred compound of the silane coupler of the present invention represented by the general formula [IV] is that R ₄ is a substituted or unsubstituted phenyl group, and cyano, nitro, or —SO is used as a substituent for the phenyl group.
₂ R ₇ (R ₇ is an alkyl group) is a compound such as a halogen atom or trifluoromethyl.

In the general formula [VI], Z and R ₁ have the same meanings as in the general formulas [IV] and [V], respectively. A preferred example of the ballast group represented by R ₁ is a group represented by the following general formula [VII].

General formula (VII) In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, l represents 0 or 1, and K
When 2 is 2 or more, two or more R _{9 s that} may be present may be the same or different, R ₈ represents a straight or branched chain having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, and R ₉ is Represents a monovalent group, preferably a hydrogen atom, a halogen atom (eg chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (eg methyl, t-butyl, t-pentyl) , T-octyl, dodecyl, pentadecyl, benzyl, phenethyl and the like), aryl group (eg phenyl group), heterocyclic group (eg contained nitrogen heterocyclic group) alkoxy group, preferably linear or branched carbon number 1
To 20 alkoxy groups (for example, groups such as methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (for example, phenoxy group), hydroxy groups, acyloxy groups, preferably alkylcarbonyloxy groups, Arylcarbonyloxy group (for example, acetoxy group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group, alkylthio group, preferably carbon An acyl group having 1 to 20 carbon atoms, preferably 1 carbon atom
To a linear or branched alkylcarbonyl group having 20 to 20 carbon atoms, an acylamino group, preferably a linear or branched alkylcarboxamide group having 1 to 20 carbon atoms, a benzenecarboxamide group, a sulfonamide group, preferably 1 to 20 carbon atoms. Straight-chain or branched alkyl sulfonamide group or benzene sulfonamide group, carbamoyl group, preferably linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, sulfamoyl group, preferably 1 to 1 carbon atoms Represents 20 linear or branched alkylaminosulfonyl groups, phenylaminosulfonyl groups, or the like.

Next, specific compound examples of the cyan coupler of the present invention represented by the general formula [IV] or [V] will be shown, but the cyan coupler is not limited thereto.

[Exemplified compound]

These cyan couplers of the present invention can be synthesized by a known method, for example, U.S. Pat. Nos. 3,222,176 and 3,4.
46,622, 3,996,253, British Patent 1,011,940, JP-A-47-21139, 56-56134, 57-204543, 57.
-204544, Japanese Patent Application Nos. 56-131309, 56-131311, and
56-131312, 56-131313, 56-131314, 56
-130459, JP-A-60-24547, 60-35731, 60
It can be synthesized by the synthetic method described in -37557 and the like.

The cyan couplers of the present invention represented by the general formulas [IV] and / or [V] may be used alone or in combination of two or more, and in the case of using the general formulas [IV] and [V] in combination, General formula (I
V] the cyan coupler of the present invention): (Cyan coupler of the present invention represented by the general formula [V]) = 1: 9 to 9: 1
Good. To add the cyan coupler of the present invention to the silver halide emulsion layer, a conventional addition method can be adopted. The addition amount is usually about 0.005 to 2 per mol of silver halide.
It is in the range of 0.01 to 1 mol, preferably 0.01 to 1 mol.

When the red-sensitive silver halide emulsion layer is composed of two or more layers separated (a non-photosensitive intermediate layer may be present between the separated red-sensitive silver halide emulsion layers), for example. When composed of two or more red-sensitive silver halide emulsion layers having different sensitivities, at least one of the red-sensitive silver halide emulsion layers may contain the cyan coupler of the present invention, but preferably all of them are contained. The red-sensitive silver halide emulsion layer contains the cyan coupler of the present invention.

Further, examples of cyan couplers that can be used in the present invention include phenol type and naphthol type couplers. And these cyan couplers are not only 4 equivalent type couplers but also 2
It may be an equivalent type coupler. Specific examples of cyan couplers that can be used in combination include U.S. Patents 2,369,929 and 2,434,2.
No. 72, No. 2,474,293, No. 2,521,908, No. 2,895,826
No. 3, No. 3,034,892, No. 3,311,476, No. 3,458,315,
3,476,563, 3,583,971, 3,591,383, 3,7
67,411, 3,772,002, 3,933,494, 4,004,92
No. 9, West German patent application (OLS) 2,414,830, 2,454,329
No. 48-59838, No. 51-26034, No. 48-5055
No. 51, No. 51-146827, No. 52-69624, No. 52-90932,
Examples thereof include those described in JP-A-58-95346 and JP-B-49-11572.

Couplers such as colored magenta or colored cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer and other photographic constituent layers of the present invention. For the colored magenta or colored cyan coupler, the description of Japanese Patent Application No. 59-193611 by the present applicant can be referred to, and for the polymer coupler, the description of Japanese Patent Application No. 59-172151 by the present applicant can be referred to.

The amount of the above-mentioned coupler that can be used in the present invention is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ mol, per mol of silver.

For incorporating the above-mentioned cyan coupler into the silver halide emulsion, the method for adding the inhibitor-releasing compound of the present invention such as the DIR compound can be referred to.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, UV absorbers, color stain inhibitors, fluorescent whitening agents, color image browning inhibitors, antistatic agents, hardeners, surface active agents described in Research Disclosure Magazine 17643. Agents, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

Examples of the support of the silver halide color photographic light-sensitive material of the present invention include transparent supports such as glass plates, polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films and polystyrene films. Alternatively, a reflective support such as baryta paper or polyethylene-coated paper may be used. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2,941,898.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers.
A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

In the present invention, it is preferable to use a black colloidal silver dispersion layer for preventing halation. The black colloidal silver dispersion layer must have a sufficiently high optical density for visible light (especially red light) with respect to incident light from the support surface of the color light-sensitive material or incident light from the emulsion surface. .
Further, it is necessary to have a sufficiently low reflectance for the incident light from the emulsion surface of the color light-sensitive material.

From the viewpoint of reflectance and the silver bleaching step, it is desirable that the fine particle colloidal silver is sufficiently fine, but since absorption becomes yellow to yellow-green and the optical density for red light does not increase, it is unavoidable that it becomes coarse particles to some extent. Therefore, it is considered that a physical phenomenon centered on the silver grains easily occurs and the silver bleaching property at the boundary with the silver halide emulsion layer deteriorates, resulting in poor desilvering. In particular, when the silver halide emulsion layer contains silver halide containing at least 5 mol% of silver iodide grains, particularly when the silver halide emulsion layer closest to the support contains at least 5 mol% of silver iodide grains. The phenomenon that the silver bleaching property deteriorates is prominent, but the method of the present invention is also effective for this.

Next, the color developing solution used in the present invention will be described.

The color developing agent of the color developing solution used in the present invention is preferably a p-phenylenediamine color developing agent,
A particularly useful aromatic primary amine color developing agent is an aromatic primary amine color developing agent having an amino group having at least one water-soluble group, and particularly preferably represented by the following general formula [VIII]. It is a compound.

General formula [VIII] In the formula, Ri ₁ represents a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group has a linear or branched carbon number of 1
Represents an alkyl group of 5 to 5 and may have a substituent. Ri ₂ and Ri ₃ represent a hydrogen atom, an alkyl group or an aryl group, and these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. At least one of Ri ₂ and Ri ₃ is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group or (CH _{2 q} O _p Ri ₄ ). The alkyl group may further have a substituent.

Ri ₄ represents a hydrogen atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent integers of 1 to 5.

Among the p-phenylenediamine type color developing agents, the p-phenylenediamine type color developing agent having an alkylsulfonamidoalkyl group bonded to the aromatic nucleus and / or amino nitrogen is preferable.

In the present invention, a particularly preferred p-phenylenediamine color developing agent is one having at least one alkylsulfonamide alkyl substituent bonded to an aromatic nucleus or an amino nitrogen, and specifically, the following exemplified compounds are typical examples. Is included as

[Exemplified compound] These color-developing agents can be used as salts of organic acids and inorganic acids, for example, salt types such as hydrochlorides, sulfates, phosphates, p-toluenesulfates, sulfites, acid salts and benzenedisulfonate. Used in.

The color developing solution of the present invention is preferably used at a pH of 9.9 or higher, more preferably 10.10 or higher, particularly preferably 10.20.
Above, the upper limit is related to the fog property of the photographic emulsion,
It is preferably used at a pH of 13 or less. And most preferably, it is used in the range of 10.2-11.0.

For significantly higher water solubility of the color developing agent, the amount used treatment liquid per preferably used in 1.5 × 10 ^-2 mol or more, more preferably 1.5 × 10 ^-2
Used in the range of ~ 15 x 10 ^-2 mol.

As the alkaline agent used for adjusting the pH of the color developing solution, sodium hydroxide, potassium hydroxide, sodium metaborate,
Examples include borax, potassium carbonate, sodium carbonate, potassium phosphate, potassium hydrogen carbonate and the like.

These alkylsulfonamidoalkyl-substituted-p-phenylenediamines and their derivatives preferably used in the present invention can be easily synthesized by the method described in Journal of American Chemical Society, Vol. 73, page 3100 (1951). .

Preferred compounds for use in the color developing solution of the present invention are sulfites. Sodium sulfite as sulfite,
There are sodium bisulfite, potassium sulfite, potassium bisulfite, etc., and it is preferable to use it in the range of 0.1 to 40 g / l, and more preferably 0.5 to 10 g / l.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above added to the color developing solution include potassium bromide, bromide such as sodium bromide,
Alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole,
Starting with development accelerators such as 1-phenyl-5-mercaptotetrazole, there are stain inhibitors, anti-sludge agents, preservatives, layer effect accelerators, chelating agents and the like.

Regarding the processing method of the photographic light-sensitive material of the present invention, after color development, a bleach-fixing treatment is further performed, followed by a stabilizing treatment or washing with water, and after color development, bleaching and fixing are performed separately, and further a stabilizing treatment with water washing is further performed. Alternatively, a method of performing washing with water; or a method of performing a stabilizing treatment after the stabilizing treatment (or washing with water) alternative to washing with water is preferable.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, aminopolycarboxylic acids or acids, organic acids such as citric acid, and those in which metal ions such as iron, cobalt and copper are coordinated are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid propylenediaminetetraacetic acid nitrilotriacetic acid iminodiacetic acid glycol etherdiaminetetraacetic acid ethylenediaminetetrapropionic acid ethylenediaminetetraacetic acid disodium salt diethylenetriaminepentaacetic acid pentasodium salt nitrilotriacetic acid sodium salt The bleaching solution and bleach-fixing solution used in the present invention are , PH 0.2 to 9.5
Can be used, preferably 4.0 or more, more preferably 5.0 or more. The treatment temperature is 20 ° C to 80 ° C, preferably 30 ° C or higher.

The bleaching solution used in the present invention may contain various additives in addition to the bleaching agent as described above (preferably a ferric organic acid complex salt). As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide. Also, pH buffers such as borate, acid salt, acetate, carbonate and phosphate, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid. Acids, alkylamines, polyethylene oxides, and the like which are known to be added to ordinary bleaching solutions can be appropriately added.

The bleach-fixing solution or the silver halide fixing agent contained in the fixing solution used in the present invention is a compound which reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, which is used in ordinary fixing processing. Typical examples are thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, high-concentration bromides and iodides. . These fixing agents can be used in an amount within a range capable of dissolving 5 g / l or more, preferably 50 g / l or more, more preferably 70 g / l or more.

The bleach-fixing solution or fixing solution used in the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid as in the case of the bleaching solution. A pH buffering agent consisting of various salts such as sodium and ammonium hydroxide can be contained alone or in combination of two or more kinds.
Further, various fluorescent whitening agents, antifoaming agents, surfactants and antifungal agents may be contained. In addition, preservatives such as hydroxyamine, hydrazine, sulfite, isomeric bisulfite, bisulfite adducts of aldehyde and ketone compounds, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid. , Organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids or stabilizers such as nitro alcohols and nitrates, solubilizing agents such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamide, An organic solvent such as dimethyl sulfoxide can be appropriately contained.

In the processing method using the processing solution of the present invention, the most preferable processing method is to bleach or bleach-fix immediately after color development, and the specific gravity of the processing solution in the step following color development is 1.1.
Although the above is preferable, bleaching or bleach-fixing treatment may be carried out after washing with water or rinsing and stopping after color development, or a pre-bath containing a bleaching accelerator for bleaching or bleach-fixing. It may be used as the preceding treatment liquid.

Processing other than color development of the silver halide color photographic light-sensitive material of the present invention, for example, bleach-fixing (or bleaching, fixing), further washing with water or stabilizing with water-washing alternative, if necessary final stabilization containing formalin and activator The treatment temperature in various treatment steps such as treatment with a liquid is preferably 20 ° C to 80 ° C, more preferably 40 ° C or higher.

In the present invention, JP-A Nos. 58-14834 and 58-105145 are used.
No. 58-134634, No. 58-18631 and Japanese Patent Application No. 58
It is preferable to carry out water washing alternative stabilization treatment as shown in No. 2709 and No. 59-89288.

The water-washing substitute stabilizer is not a normal stabilizing treatment but a water-washing substitute treatment, and in addition to the above, an image stabilizing treatment as described in JP-A-58-134636 is applied to substantially eliminate the washing treatment. It is for. Therefore, the name of the treatment bath does not necessarily have to be stabilization treatment.

As the stabilizing solution, there is a stabilizing solution having a function of stabilizing a color image and a function of a draining bath function to prevent contamination such as uneven washing with water. In addition, a color adjusting liquid for coloring a color image and an antistatic liquid containing an antistatic agent are also included in these stabilizing liquids.
When bleaching or fixing components are brought into the stabilizing solution from the pre-bath, they are neutralized, desalted and inactivated to prevent deterioration of the storability of the dye.

As a component contained in such a stabilizing solution, a chelate stability constant with iron ion is 6 or more (particularly preferably 8 or more).
There are chelating agents that are. These chelating agents include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, polyhydroxy compounds, inorganic phosphoric acid chelating agents and the like. Among them, preferable chelating agents include ethylenediamine diorthohydroxyphenylacetic acid, nitrilotriacetic acid, Hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2 -Carboxylic acid, 2-phosphonobutane-1,2,4
-Tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, For effect, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof are particularly preferable. These compounds generally have a concentration of about 0.1 g to 10 g with respect to Stabilizer 1, more preferably Stabilizer 1.
Used in a concentration of about 0.5 g to 5 g.

The compound added to the stabilizing solution is an ammonium compound. These are supplied by ammonium salts of various inorganic compounds. Specifically, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluorinated ammonium, etc. Ammonium, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, lauryl tricarboxylic acid Ammonium acid, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, hydrogen malate Ammonium, ammonium hydrogen oxalate, ammonium hydrogen phthalate,
Ammonium hydrogen tartrate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidinedithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, thioglycolic acid Examples include ammonium and 2,4,6-trinitrophenol ammonium. The amount of these ammonium compounds added is in the range of 0.05 to 100 g, preferably 0.1 to 20 g per stabilizer.

As the compound added to the stabilizing solution, acetic acid, sulfuric acid, hydrochloric acid, nitric acid, sulfanilic acid, potassium hydroxide, sodium hydroxide, pH adjusting agents such as ammonium hydroxide, sodium benzoate, butyl hydroxybenzoate, antibiotics, Tehydroacetic acid, potassium sorbate, thiapentazole, ortho-phenylphenol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 1,2-benzisothiazoline Other than 3--3-one, Japanese Patent Application No. 59-146325 (pages 26 to 30) describes antifungal agents, preservatives such as water-soluble metal salts, ethylene glycol, polyethylene glycol, polyvinylpyrrolidone (PVP K-15, And a dispersant such as Viscole K-17), a hardener such as formalin, and an optical brightener. Among these additive compounds, the ammonium compound described in Japanese Patent Application No. 58-58693 has a function of adjusting to a weak acidity optimum for pH preservation in the image film. The compound used together with the ammonium compound is an acid, and sulfuric acid, hydrochloric acid or the like is used.

Particularly, in the present invention, a water-washing substitute stabilizing solution containing the above anti-fungal agent is particularly preferably used.

The pH value of the stabilizing solution is adjusted to 0.1 to 10, preferably 2 to
9, more preferably at pH 4-8.5. In addition, it is preferable that the stabilization treatment step is performed in a multi-stage tank, and the replenisher is replenished from the last-stage tank, and the back-flow system in which the replenisher is sequentially overflowed into the previous-stage tank can reduce the replenishment amount. Although the washing treatment is not required at all after the stabilization treatment, rinsing by a small amount of washing in a very short time, surface washing, etc. may be performed as needed.

When the stabilizing process is carried out directly after the fixing or bleach-fixing process without substantially passing through the washing process, a short silver recovery or a silver recovery between the fixing or bleach-fixing bath and the stabilizing bath may be performed. Rinsing with accumulated water may be provided. After the stabilizing treatment, a water-removing bath containing a surfactant may be provided, but preferably a silver recovery bath, a rinse, a water-removing bath, etc. are not provided. These additional treatments may be spraying or smearing treatments.

The light-sensitive material to which the present invention is applied is for a film, and an aldehyde derivative may be added to the negative stabilizer in order to improve the storability of photographic images.

If necessary, various additives are added to the negative stabilizing solution, for example, a water drop unevenness preventing agent such as a siloxane derivative, boric acid, citric acid, phosphoric acid, acetic acid, or pH of sodium hydroxide, sodium acetate, potassium citrate, or the like. Conditioning agents, hardeners such as potassium alum, black alum, methanol, ethanol,
Organic solvents such as dimethylsulfoxide, humidity controlling agents such as ethylene glycol and polyethylene glycol, and other additives such as color toning agents for improving or extending the treatment effect may be added.

Also, the negative stabilizing solution may be divided into two or more compartments in order to increase the length of the countercurrent flow path, as in the above-described stabilizing solution.
The method of preparing the replenishing solution and the replenishing amount may be the same as those in the case of the stabilizing solution.

The processing method according to the present invention is applied to a color negative film, a color positive film, a slide color reversal film, a movie color reversal film, and a TV color reversal film. Particularly, silver iodobromide or silver chloroiodobromide containing 0.5 mol% or more of silver iodide with a total coating silver amount of 25 mg / dm ² or more, further 30 to 15
0 mg / dm ^2, in particular the most suitable for processing of high speed color film is 35 to 100 mg / dm ^2.

[Advantages of the Invention] According to the present invention, the object of the present invention can be achieved, stable treatment can be achieved without fogging even after continuous treatment for a long period of time, and even when a DIR coupler is used. It is possible to provide a method for processing a silver halide color photographic light-sensitive material which has good desilvering performance and in particular has improved image quality such as graininess.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Reference Example 1 An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion. The layers were coated so that the total silver content was 62 mg per 100 cm ² . The above emulsion layer is silver iodobromide having a mol% of silver iodide of about 4.8%. In this case, α- (4-nitrophenoxy) -α-pivalyl was used as a yellow coupler in the blue-sensitive silver halide emulsion layer. -5- [γ
-(2,4-Di-t-aminophenoxy) butyramide] -2-
Chloroacetanilide was used, and 1- (2,4,6-trichlorophenyl) -3-{[α- (2,4-di-t-amylphenoxy)-was used as a magenta coupler in the green-sensitive silver halide emulsion layer. Acetamido] benzamido} -3-pyrazolone and 1- (2,4,6-trichlorophenyl) -3-{[α- (2,4-
Di-t-amylphenoxy) -acetamido] benzamido} -4- (4-methoxyphenylazo) -5-pyrazolone, and the following (C-i) as a cyan coupler in the red-sensitive silver halide emulsion layer: Ordinary additives such as sensitizing dyes and hardeners were added to each emulsion layer. However, to the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, the DIR compound according to the present invention shown in Table 1 was added in an amount of 0.4 × 10 ^-2 mol of 1 mol of the halogen-sensitive material silver, and the film sample was prepared. Experiments were performed using.

Cyan coupler (C-i) This film sample was subjected to white step exposure using a KS-7 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) and processed according to the following steps.

Processing process (38 ℃) Number of tanks Processing time Color development 1 tank 3 minutes 15 seconds Bleach 1 tank 3 minutes 15 seconds Fixed 1 tank 3 minutes 10 seconds Water washing alternative stable 2 tanks 1 minute 20 seconds (cascade) Clean 1 tank The composition of the color developer used for 30 seconds is as follows.

Potassium carbonate 28g Sodium hydrogen carbonate 2.5g Potassium sulfite 3.0g Sodium bromide 1.2g Potassium iodide 1.2mg Hydroxylamine derivative (shown in Table 1) 3.0g Diethylenetriamine sodium pentaacetate 2.0g 4-Amino-3-methyl-N-ethyl- N- (β-hydroxyethyl) aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

The composition of the color developing replenisher used is as follows.

Potassium carbonate 30g Sodium hydrogen carbonate 1.0g Potassium sulfite 4.3g Sodium bromide 0.9g Hydroxylamine derivative (shown in Table 1) 3.0g Diethylenetriamine sodium pentaacetate 2.5g 4-Amino-3-methyl-N-ethyl-N- (β- Hydroxyethyl) aniline sulfate 5.5g Potassium hydroxide 1.4g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

The compositions of the bleaching solution and the bleaching replenisher used are as follows.

Ethylenediaminetetraacetate Ammonium iron (III) 100g Ammonium bromide 140g Add water to make 1 and use glacial acetic acid and aqueous ammonia.
Adjust to pH 5.8.

The compositions of the washing substitute fixing solution and the fixing replenisher used are as follows.

Ammonium thiosulfate 180g Anhydrous sodium sulfite 12g Potassium hydroxide 1g Sodium carbonate 8g Add water to make 1 and adjust to pH 7.0 with concentrated aqueous ammonia or acetic acid.

The stabilizing solution and stabilizing replenisher used are as follows.

2-Ethyl-4-isothiazolin-3-one 0.1g Ethylene glycol 1g Add water to make 1.

The cleaning solution and cleaning replenisher used are as follows.

Add water to make 1.

A running test was performed using the treatment liquid. The replenishing amount of each replenisher was 600 ml per 1 m ^{2 of} film sample for color development and stability, 300 ml per 1 m ^{2 of} film sample for bleaching, and 700 ml per 1 m ^{2 of} film sample for fixing and cleaning. In this running test, processing was carried out discontinuously until the total replenishing amount of the bleaching replenishing solution became three times the tank volume of the bleaching treatment tank. After the running test, the green density of the non-exposed portion of each processed film sample was measured using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Rokusha Kogyo KK).

Further, the residual silver amount in the highest density portion of the processed film sample was measured by the fluorescent X-ray method. The results are summarized in Table 1.

From Table 1 above, there is a drawback that the desilvering performance is deteriorated when the DIR compound is used, and the green density in the unexposed area, that is, the fog is increased when the hydroxylamines are not used. It can be seen that the use of hydroxylamine, which is frequently used in the color developing solution, makes it impossible to obtain sufficient desilvering performance or good unexposed portion transmission green density (M fog). Furthermore, only when the DIR compound and hydroxylamines according to the present invention are used in combination, the desilvering performance and the unexposed portion transmission gulin concentration (M
It can be seen that both performances (fog) are good.

Reference Example 2 In the sample used in Experiment No. 6 of Reference Example 1, only the silver iodide content of each photosensitive silver halide emulsion layer was 0.1 mol%,
Samples that differ only in that they were changed to 0.5 mol%, 2.1 mol%, 3.1 mol%, 7.9 mol%, 14.9 mol%, and 30 mol% were prepared, subjected to the same exposure / running processing as in Reference Example 1, and unexposed. Partial transmission green concentration and residual silver amount were measured, and green concentration residual silver amount (mg / dm ² )… 0.60 0.3… 0.57 0.3… 0.55 0.4… 0.53 0.4… 0.52 0.4… 0.52 0.7… 0.52 1.2 (however, The result was that the green density of the density part was insufficient.).

As is clear from these results, the silver halide color photographic light-sensitive material to be processed according to the present invention preferably has a silver iodide content of the photosensitive layer of 0.5 mol% or more from the viewpoint of suppressing development fog. It is found that the content is preferably 2 mol% or more and 15 mol% or less, particularly 3 mol% or more and 8 mol% or less.

Reference Example 3 In Experiment No. 16 of Reference Example 1, the color developing agent [4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline] of the color developer and replenisher used for the processing Sulfate] was changed to the following No. exemplified compounds (1), (2), (3), (6), and the same exposure and running treatments as in Reference Example 1 were carried out to transmit the unexposed portion. When the green density and graininess (RMS) were measured, the former fogging was 0.53, 0.52, 0.53, and 0.53, and the latter grain was 49, 47, 49, and 51. Was obtained. The granularity of Experiment No. 16 of Reference Example 1 was 56.

However, the granularity (RMS) of the color image with a color image density of 1.0
It was carried out by comparing 1000 times the standard deviation of the variation of the density value caused when scanning with a microdensitometer having a circular scanning aperture diameter of 25 μm.

Reference Example 4 In the sample used in Experiment No. 6 of Reference Example 1, a cyan coupler in the red-sensitive silver halide emulsion layer was used as an exemplified compound (C-
1), (C-3), and (C-8) were changed to prepare different samples and subjected to the same exposure / running process as in Reference Example 1, and the transmission green density of the unexposed area and the cyan stain generation state. Of the former was 0.50 ... 0.50 ... 0.49, and the latter cyan stain was slightly observed in the former sample No. 6 (0.02).
However, none of the above and was observed.

Reference Example 5 In the sample used in Experiment No. 6 of Reference Example 1, the hydroxylamine derivative and the DIR compound were (I-2) + (D'-2) (I-8) + (D'-13) ( I-2) + (D'-25) (I-20) + (D'-40) (I-10) + (D-1) (I-2) + (D-7) Samples differing only in that were prepared, subjected to the same exposure and running treatment as in Reference Example 1, and the transmission green density of the unexposed area and the residual silver content of the highest density area were measured. dm ² ) ... 0.54 0.4 ... 0.55 0.5 ... 0.54 0.4 ... 0.54 0.4 ... 0.54 0.5 ... 0.55 0.6.

Example 1 A tabular silver halide emulsion was prepared with reference to JP-A-58-113934 (Example emulsions 2, 3, and 4), and the following photographic materials were self-produced.

On the polyethylene terephthalate film support, a multi-layer color light-sensitive material sample composed of each layer having the following composition was prepared.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion layer Odor Silver iodide (silver iodide: 3.5 mol% monodisperse spherical particles having an average particle size of 0.3 μm) ... Silver coating amount 0.8 g / m ² Silver iodobromide (silver iodide: 3 mol% average particle thickness 0.2 μm Average particle size 4.0 μm Tabular grains) Silver coating amount 0.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per 1 mol of silver Sensitizing dye II: 1 mol of silver 1.5 × 10 ^-5 mol Cyan coupler (exemplary compound C-1): 0.044 mol per 1 mol of silver Fourth layer: second red-sensitive emulsion layer Silver iodobromide (silver iodide: 7 mol%) Spherical particles having an average particle size of 1.0 μm) Silver coating amount 2.0 g / m ² Sensitizing dye I: 3.5 × 10 ⁻⁵ mol per 1 mol of silver Sensitizing dye II: 1 mol of silver 1.0 × 10 ^-5 mol cyan coupler for (eg Compound C-1): 0.020 mol per mol of silver Fifth layer: intermediate layer Same as second layer Sixth layer: first green-sensitive emulsion layer Silver iodobromide (silver iodide: 4.2 mol% average) Spherical polydisperse emulsion with a grain size of 0.34 μm) ・ ・ ・ Silver coating amount 1.8 g / m ² Sensitizing dye III ・ ・ ・ 3.3 × 10 ^-5 mol per 1 mol silver Sensitizing dye IV ・ ・ ・ Silver 1 1.1 × 10 ^-5 mol per mol Magenta coupler of Reference Example 1 ... 12 per mol of silver
g 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide (Silver iodide: 4.2 mol% Average grain thickness 0.25 μm,
Average particle size 6.0μm tabular grain) ・ ・ ・ Silver coating amount 1.8g / m
² Sensitizing dye III: 2.65 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 0.89 × 10 ^-5 mol per mol of silver Magenta coupler of Reference Example 1: silver 1 0 per mole.
02 mol Eighth layer: Yellow filter layer Gelatin layer containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone in aqueous gelatin solution Ninth layer: First blue-sensitive emulsion layer Iodobromide Silver (silver iodide: 5.6 mol% spherical particles having an average particle size of 0.3 μm) Yellow coupler of Reference Example 1 ...
25 mol 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (silver iodide: 6 mol% spherical particles having an average particle size of 0.76 μm) ... Silver coating amount 1.21 g / m ² Yellow coupler of Reference Example 1 ... 0 for 1 mole of silver
06 mol 11th layer: 1st protective layer Silver iodobromide (silver iodide: 1 mol% average particle size 0.07 μm)
Silver coating amount 0.5 g Gelatin layer containing emulsified dispersion of UV absorber 12th layer: 2nd protective layer Gelatin layer containing trimethyl methacrylate particles (diameter 1.5 μm) In addition to the above composition, each layer contains a gelatin hardening agent. And surfactants were added.

Sensitizing dye I: Anhydro-5,5'-dichloro-3,3-di-
(Γ-Sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: Anhydro-9-ethyl-3,3'-di- (γ-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: Anhlo-9-ethyl-5,5'-dichloro-
3,3'-Di- (γ-sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: Anhydro-5,6,5 ', 6'-tetradichloro-1,1'-diethyl-3,3' -Di- {β- [β- (γ-sulfopropoxy) ethoxy]} ethyl imidazolocarbocyanine hydroxide sodium salt Experiment N of Reference Example 1 using the sample prepared as described above.
It was exposed and running as in o.6 (No.30). As a result, it was confirmed that the effect of the present invention was remarkably greater than that of the conventional photographic material when tabular silver halide grains were used as described below.

Green concentration Residual silver amount (mg / dm ² ) Experiment No. 6 0.52 0.4 Experiment No. 30 0.50 0.2 Reference Example 6 Instead of the DIR compound used in Reference Example 1, the exemplified compound (II
-2), (II-5), (III-1), and (III-3) were used, and the same experiment as in Reference Example 1 was performed.

As a result, the transmission green density in the unexposed area deteriorated by about 0.02, but the desilvering performance was the same, and there was no problem in practical performance.

Example 2 For the red-sensitive silver halide emulsion layer or the green-sensitive silver halide emulsion layer in the film sample used in Example 1, the DIR compound according to the present invention was used in the same manner as in Example 1 but 0.4 × per mol of silver halide. A sample with 10 ^-2 mol added and a sample without added were prepared. Further, an experiment was conducted using tabular grains or monodisperse spherical grains (average grain size 0.3 μm) in which silver halide grains in the third and seventh layers of these samples had the same silver halide composition and amount of silver. A sample for use was prepared and used for the experiment.

Further, the hydroxylamine derivative in the color developing solution was changed as shown in Table A below, and an experiment was conducted.

The results are summarized in Table A below.

From Table A above, it can be seen that the effects of the present invention are remarkable when a specific DIR compound, a specific hydroxylamine derivative and tabular halogenated grains are used in combination.

Front page continuation (72) Inventor Masao Ishikawa 1 Sakura-cho, Hino City, Tokyo Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-52-153437 (JP, A) JP-A-53-32035 (JP) , A) JP 59-197037 (JP, A) JP 63-5341 (JP, A) US Patent 3823017 (US, A) US Patent 3615563 (US, A) US Patent 3227554 (US, A)

Claims (1)

[Claims] 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material having a transparent support with a color developer, wherein the light-sensitive material is represented by the following general formula [I] or ( D-1) and at least one of the silver halide emulsion layers contains tabular silver halide grains containing 0.5 mol% or more of silver iodide, and the color developing solution contains A method of processing a silver halide color photographic light-sensitive material, which comprises a compound represented by the following general formula [A]. General formula [A] (In the formula, R and R'are each a hydrogen atom and a carbon number of 1 to 5
Represents an unsubstituted alkyl group or a substituted alkyl group. However, R and R'are not hydrogen atoms at the same time, and R and R'may be bonded to each other to form a nitrogen-containing heterocycle together with> N-. General formula [I] A ₁ -Z ₁ (In the formula, A ₁ is a coupler component capable of coupling with an oxidized product of a p-phenylenediamine color developing agent, and Z ₁ is a reaction with a p-phenylenediamine color developing agent. To leave,
The components that suppress the development of silver halide are shown below. ) General formula (D-1) AY) _m (In the formula, A represents a coupling component, m represents 1 or 2, Y couple | bonds with the coupling position of the coupling component A, p,
-Represents a group that is released by a reaction with an oxidant of a phenylenediamine color developing agent and becomes a development inhibitor having a large diffusibility or a compound capable of releasing a development inhibitor. )