JP2992823B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention has good desilvering properties even when a bleach-fix solution is replenished at a low level, and has a high bleaching stain. It concerns a small processing method.

[Conventional technology]

In color development, the 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. In addition, components such as heavy metal ions contained in other processing solutions are also brought into the color developing solution and accumulated by so-called back contamination.

A color developing solution used for such color developing is usually
Sulfite or a water-soluble salt of sulfite and hydroxylamine is added as a preservative (antioxidant) to increase its preservative properties. Of the above, fogging occurs remarkably with the lapse of time when the sulfite alone is used, as in the former, and the preservation of the developer is achieved by using the sulfite and the water-soluble salt of hydroxylamine together as in the latter. Is significantly increased, and the occurrence of fog due to aged developer is reduced.

However, recently, there is a tendency to reduce the concentration of sulfurous acid in the color developing solution due to a problem in rapid processing. For that reason,
There is a problem that hydroxylamine is rapidly oxidized and the preservability of the color developing solution is reduced. For this purpose, various techniques have been studied which have a sufficient preserving ability even under a low sulfurous acid concentration. For example, 2-anilinoethanol and dihydroxyalkene have been proposed in U.S. Pat. Nos. 3,823,017 and 3,615,503, respectively. However, all of these compounds are unstable per se and have no preservative effect in a color developing solution.

On the other hand, in a developer (for black-and-white photographs) containing hydroquinone or N-alkyl-p-aminophenol as a developing agent, saccharose (sucrose) is known as a preservative, but saccharose is an aromatic primary amine. Has little effect as a preservative in a color developing solution containing as a developing agent.

In addition, ascorbic acid and its derivatives are known as preservatives for black-and-white photographic developers and color formers, but they have the drawback of inhibiting color development and causing a significant decrease in color density. Inferior to hydroxylamine.

Further, α-hydroxy aromatic alcohols described in JP-A-52-7779, hydroxamic acid compounds described in JP-A-52-27638, α-aminocarbonyl compounds described in JP-A-52-143020, and JP-A-52-102727 are described. And the amino acid derivative described in JP-A-52-140324 are disclosed.

However, when used in large amounts, monosaccharides and amino acid derivatives show considerable preservation at room temperature, but are easily decomposed by heat and have undesirable characteristics in terms of pollution.

D-glucosamine hydrochloride is known as a typical α-aminocarbonyl compound, but this compound is inferior to hydroxylamine in preservation.

Hydroxamic acid compounds have the same level of preservability as hydroxylamine, but have the disadvantage of high cost.

JP-B-61-48698 and JP-B-61-48699 disclose a method in which a bisulfite adduct of an aldehyde is used in a color developing solution. The bisulfite-added compound of aldehyde shows a certain degree of preservation even when used alone, but its preservation ability is insufficient.

JP-A-63-11938 and JP-A-62-246048,
Derivatives of hydroxylamine are disclosed. Hydroxylamine derivatives are good compounds in that rapid processing and preservation can be achieved simultaneously when processing a silver halide color photographic light-sensitive material containing a high silver chloride emulsion.

On the other hand, in recent years, low replenishment of a color developing solution has been performed mainly for low pollution and low cost.
In the specification of Japanese Patent No. 552, a photographic light-sensitive material in which silver halide has an extremely high silver chloride content is treated with a small replenishment amount such that overflow does not occur even when replenished, so that elution of bromide ions is reduced, resulting in bromide. There has been proposed a processing method that does not require high-temperature processing because ions do not have a high concentration.

However, in order to reduce pollution and cost, it is necessary to reduce the amount of the bleach-fixing solution to be lower than that of the color developing solution. However, in practice, the amount of the bleach-fixing solution is not easily reduced. The main reason is that the retention time is prolonged due to the low replenishment, so that tar is generated, stain is easily generated due to the reduction of sulfurous acid, the mixing ratio of the color developing solution is increased, and the desilvering property is reduced. It is thought to be due to such problems.

The present inventors have conducted intensive studies in view of the above problems, and as a result, the silver halide color photographic light-sensitive material containing a high silver chloride emulsion has a desilvering property even when the mixing ratio of the color developing solution in the bleach-fix solution is high. The use of a hydroxylamine derivative in the color developing solution makes it difficult to generate stains, and is particularly effective when the replenishment of the bleach-fixing solution is reduced, and more surprisingly, the bleach-fixing solution. The present inventors have found that the preservation property of the polymer is also improved.

[Object of the invention]

Accordingly, an object of the present invention is to firstly provide a technique capable of obtaining stable photographic performance even when the bleach-fix solution is replenished at a low level, and secondly to provide a stable bleach-fix solution processing method. Thirdly, it is an object of the present invention to provide a processing method for preventing stain in the bleach-fix solution.

[Configuration of the invention]

An object of the present invention is to provide a silver halide color photograph having at least one silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more and a nitrogen-containing heterocyclic mercapto compound on a support. When the photosensitive material is subjected to bleach-fixing after color development, the color developer is a hydroxylamine derivative represented by the following general formula (I) and 3.
The color developing solution contains 0 × 10 ^-2 mol / or more chloride, and the replenishing amount of the color developing solution is 30 to 180 m per 1 m ^{2 of the} light-sensitive material, and the replenishing amount of the bleach-fixing solution is 1 m ² per 1 m ^{2 of the} light-sensitive material. 100m
The present inventors have found that this is achieved by a method for processing a silver halide color photographic light-sensitive material characterized by the following.

[Wherein, R ¹ and R ² each represent an alkyl group or a hydrogen atom. However, both R ¹ and R ² are not hydrogen atoms at the same time. R ¹ and R ² may form a ring. Hereinafter, the present invention will be described in detail.

In the general formula (I), R ₁ and R ₂ each represent an alkyl group or a hydrogen atom that is not a hydrogen atom at the same time, but the alkyl groups represented by R ₁ and R ₂ may be the same or different, and Alkyl groups of formulas 1 to 3 are preferred. The alkyl groups of R ₁ and R ₂ include those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, forming a heterocyclic ring such as piperidine, piperazine or morpholine. Is also good.

Specific compounds of the hydroxylamine derivative represented by the general formula [I] are described in U.S. Patent Nos. 3,287,125 and 3,293,0
No. 34, No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

The compound represented by the general formula [I] and hydroxylamine are usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

The concentration of the hydroxylamine derivative represented by the general formula [I] is 2 × 10 ^{-3 to} 5 × 10 ^-1 mol per color developing solution,
It is preferably from 5 × 10 ^-3 mol to 3 × 10 ^-1 mol, particularly preferably from 1 × 10 ^-2 mol to 1.5 × 10 ^-1 mol.

Further, a small amount of hydroxylamine may be added in addition to the hydroxylamine derivative represented by the general formula [I]. Specifically, 1.5 × 10 ⁻¹ mol / or less is preferably used, but this is effective in suppressing precipitates and precipitates in the color developing solution.

By containing chloride and / or bromide in the color developing solution of the present invention, the replenishment can be reduced and the stability of processing (fluctuations in the minimum density and fluctuations in the maximum density) can be improved. Chloride is 3.0
The effect of the present invention is remarkably exhibited by containing at least ^10-2 mol / mol.

That is, the chloride exhibits a mild inhibitory effect on the high silver chloride emulsion unlike the bromide, so that the chloride is stabilized by being present in a certain amount in the color developing solution. Chloride is added in the form of lithium chloride, magnesium chloride, potassium chloride, sodium chloride.

The chloride is preferably added in advance, and as a result, the total amount should be 3.0 × 10 ^-2 mol / or more in combination with the amount of chloride eluted from the silver chloride emulsion.

Bromide, high use silver chloride emulsion 1.0 × 10 ^-3 mol / or less In the case of conducting rapid processing within 1 minute, 1.0 × 10 ^-3 mol / or bromide in the case of performing the processing of more than one minute Concentration is required. Because bromide has a strong inhibitory effect,
In the case of rapid processing for 1 minute or less, the processing variability is large, and sufficient rapidity cannot be obtained. Also, in order to apply a high silver chloride emulsion to a variety of existing automatic developing machines, that is, to perform processing for 1 minute or more, fog cannot be suppressed only by chloride,
1.0 × 10 ^-3 mol / or more of bromide is required. 1.0 ×
By containing 10 ^-3 mol / m or more of bromide, there is an effect of preventing stain in the bleach-fix solution to some extent.

The concentration of sulfurous acid in the color developing solution of the present invention is preferably 2.0 × 10 ⁻² mol / or less, more preferably 1.5 × 10 ⁻² mol / or less, and particularly preferably 1.0 × 10 ⁻² mol / or less.

That is, the concentration of sulfurous acid in the color developer greatly affects the color density of a color photographic light-sensitive material using a high silver chloride emulsion, and even if the development time is slightly increased (for example, 3 minutes and 30 seconds), the decrease in the maximum density is not affected. Occurs. Therefore, it is necessary to keep the concentration within the above range, but the color developing solution of the present invention has sufficient preservation even at a low sulfurous acid concentration. The effect of the present invention is particularly remarkable when the sulfurous acid concentration is low.

In order to contain the sulfite ion at the above concentration, the sulfite ion may be added as a compound such as a bisulfite adduct of an aldehyde or a water-soluble sulfite such as sodium sulfite or potassium sulfite.

The color developing solution of the present invention preferably contains a chelating agent from the viewpoint that the above-mentioned object of the present invention can be more highly achieved. That is, the deterioration of the color developing solution due to the incorporation of heavy metal ions is prevented, and the preservability is improved. Preferred chelating agents include aminopolycarboxylic acids, organic phosphonic acids, and tiron derivatives. In particular, a Tyrone derivative is preferably used in the sense that precipitation with Ca or Mg in a color developing solution is hardly caused.

The aminopolycarboxylic acid is represented by the following general formula [II], and the organic phosphonic acid is represented by the following general formula [III] or [IV].

(Wherein, E is an alkylene group, a cycloalkylene group, a phenylene _{group, -B 5 -O-B 5 -} , - B 5 -O-B 5 -O-B 5 - or -B ₅ -Z-B ₅ - Z is NB ₅ -A ₅ , NA ₅ or Represents B _{1 to} B ₆ each represent an alkylene group. A _{1 to} A ₃
Represents —COOM or —PO ₃ (M) ₂ , A ₄ and A
₅ is a hydrogen atom, a hydroxyl group, —COOM or —PO ₃ (M) ₂
Represents M represents a hydrogen atom or an alkali metal atom. ) (In the formula, B ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group; M represents a hydrogen atom or an alkali metal atom.) (Wherein B ₈ , B ₉ and B ₁₀ are each a hydrogen atom, a hydroxyl group, -CO
OM, —PO ₃ (M) ₂ or an alkyl group, wherein L ₁ , L ₂ and L ₃ are each a hydrogen atom, a hydroxyl group, —COOM, —PO ₃ (M)
₂ or Represents J represents a hydrogen atom, an alkyl group, a -C ₂ H ₄ OH or -PO _{3 (M) 2.} M represents a hydrogen atom or an alkali metal atom, and n and m each represent 0 or 1. Some specific examples of the chelating agent represented by the general formula [II], [III] or [IV] are shown below. The chelating agent used in the present invention is not limited to the following specific examples.

The chelating agents represented by the general formulas (II) to (IV) are preferably used in an amount of 0.01 g to 100 g, more preferably 0.05 g to 50 g, and particularly preferably 0.05 g to 1 g of the color developing solution of the present invention. 0.1 g to 20 g.

The Tyrone derivative is a compound represented by the following general formulas [V] to [VIII].

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -OR ₁₉ , -COOR ₂₀ , Or a substituted or unsubstituted phenyl group. R ₁₉ , R ₂₀ ,
R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. n represents an integer of 1 to 3. R ₁₅ may be the same or different. R ₁₅ is preferably a sulfonic acid group.

In the formula, R ₂₃ and R ₂₄ represent a hydrogen atom, a halogen atom or a sulfo group.

In the formula, R ₂₉ and R ₃₀ each represent a hydrogen atom, a phosphate group, a carboxylic acid group, —CH ₂ COOH, —CH ₂ PO ₃ H ₂ or a salt thereof, and X ₃
Represents a hydroxyl group or a salt thereof, and W ₁ , Z ₁ and Y ₁ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof, an alkoxy group or an alkyl group. Represents M ₃ is 0 or 1,
n ₃ is an integer of 1 to 4, l ₁ is 1 or 2, p ₂ is an integer of 0 to 3,
q ₁ represents an integer of 0 to 2.

Specific examples of the chelating agents represented by the general formulas [V] to [VIII] include the following.

Among the chelating agents represented by the general formulas [V] to [VIII], it is more effective to use a chelating agent represented by [V] or [VIII], and more preferably, a general formula [VII
The chelating agent represented by I] is used. It is particularly preferable to use the chelating agent represented by the exemplified chelating agents (45), (49) or (54). These chelating agents can be used in combination of two or more kinds.

The general formulas [V] to [VI] preferably used in the present invention.
II] is a color developing solution 1
It is preferably added in the range of 1 × 10 ^-4 mol to 1 mol, more preferably 2 × 10 ^-4 mol to 1 × 10 ^-1 mol, more preferably 5 × 10 ^-4 mol. ^-4 mol to 5 × 10 ^-2 mol can be added.

As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of obtaining the effects of the present invention.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material than the p-phenylenediamine-based compound having no water-soluble group, such as N, N-diethyl-p-phenylenediamine, and has an effect on skin. It also has the advantage that the skin is less susceptible to irritation.

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble _{group, - (CH 2) n-} CH 2 OH, - _{(CH 2) m-NHSO 2} - (CH 2) n-CH 3, - (CH 2) m-O- (CH 2) n-CH 2, - (CH 2 CH 2 O) nCmH 2 m 1 (m and n represents an integer of 0 or more, respectively), -. COOH group, be mentioned as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the invention are shown below.

The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, p-toluenesulfonate, and usually in the range of 1 × 10 ^-3 mol to 2 × 10 ^-1 mol per color developer. It is preferably used, but more preferably in the range of 1.5 × 10 ^-3 mol to 2 × 10 ^-1 mol per chromogenic image solution from the viewpoint of rapid processing.

The color developing solution of the present invention may contain the following developing solution components in addition to the above components.

Examples of the alkaline agent include sodium carbonate and potassium carbonate. Sodium hydroxide, potassium hydroxide, silicate,
Sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, boric acid and the like can be used alone or in combination. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. be able to.

If necessary, inorganic and organic antifoggants can be added.

Furthermore, if necessary, a development accelerator can be used. U.S. Pat.No. 2,648,604 as a development accelerator
No. 3,671,247, JP-B-44-9503, various kinds of pyridinium compounds, other cationic compounds, cationic dyes such as phenosafuran, neutral salts such as thallium nitrate, U.S. Pat. Nos. 2,533,990, 2,531,832, 2,950,970, 2,577,127 and JP-B-44-9504, polyethylene glycol and derivatives thereof, nonionic compounds such as polythioethers, and JP-B-44-9509. The organic solvents described above are included. Also described in U.S. Patent No. 2,304,925 benzyl alcohol, phenethyl alcohol and others,
Examples include acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines.

Further, the color developing solution of the present invention may contain, as necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509. An organic solvent for increasing the solubility of the developing agent can be used.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl -P-Phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 10 g /. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound and the like can be added.

Furthermore, various additives such as other stain inhibitors, sludge inhibitors, and layering effect promoters can be used.

In the color developing solution of the present invention, it is preferable to use a triazylstilbene-based fluorescent whitening agent from the viewpoint of preventing the generation of tar, and the triazylstilbene-based fluorescent whitening agent is represented by the following general formula (IX). The compounds shown are preferably used.

In the formula, X ₁₁ , X ₁₂ , Y ₁₁ and Y ₁₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy and the like),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
An aryl group (eg, phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β
-Hydroxyethyl)) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino,
N- (β-hydroxyethyl-N ′ methylamino and the like),
Arylamino group (for example, anilino, o-, m-, p-
Sulfoanilino, o-, m-, p-chloroanilino, o
-, M-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specific examples include the following compounds, but are not limited thereto.

The above-mentioned triazyl stilbene-based brightener is described in, for example, "Fluorescent Brightener" edited by the Chemical Industry Association of Japan (issued in August 1976).
It can be synthesized by the usual method described on page.

These triazylstilbene-based brighteners are preferably used in the range of 0.2 g to 20 g, and particularly preferably in the range of 0.4 g to 10 g, per color developing solution of the present invention.

Each component of the color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, it can be obtained by adding a plurality of components, each of which can stably coexist, to a concentrated aqueous solution or a solution prepared in advance in a small container in a solid state in water and stirring to prepare the solution.

Although the color developing solution of the present invention can be used in an arbitrary pH range, it is preferably pH 9.5 to 13.0 from the viewpoint of rapid processing,
More preferably, it is used at pH 9.8 to 12.0.

The processing temperature of color development using the color developing solution of the present invention,
The temperature is 30 ° C. or more and 50 ° C. or less, and the higher the temperature, the more rapid processing can be performed in a shorter time, which is preferable. However, on the contrary, there is a problem that the preservability tends to deteriorate.

The replenishment amount of the color developing solution is 300 m to 1 per m ² of the photographic material.
Although the processing can be performed in the range of 0 m, in order to maximize the effect of the present invention, the processing is performed in the range of 180 m to 30 m. Particularly preferably in the range of 160 m to 50 m,
Most preferably, it is processed in the range of 120 m to 80 m.

The replenishing amount of bleach-fixing solution used in the present invention but is less than the silver halide color photographic light-sensitive material 1 m ² per 100 m, preferably 15M～100m, particularly preferably 30 to 1
00m. If it is less than 15m, the liquid level will drop due to evaporation,
The bleach-fixing properties are significantly reduced and the stain is greatly increased.

When the replenishment amount exceeds 200 m per 1 m ^{2 of the} silver halide color photographic light-sensitive material, the effect of the present invention is hardly remarkably exhibited, and when the replenishment amount is 100 m or less, a remarkable effect is observed.

As the bleaching agent used in the bleach-fixing solution of the present invention, a metal complex salt of an organic acid is preferably used, and the metal complex salt oxidizes metal silver formed by development to silver halide and, at the same time, does not use a color forming agent. It has an action of coloring the coloring portion, and has a structure in which metal ions such as iron, cobalt, and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetra acetic acid [10] Glycol ether amine tetra acetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra (trimethyl ammonium) salt [15] ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)
-N-N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetate sodium salt The bleaching solution used is an organic acid as described above. And a variety of additives. As the additive, it is particularly desirable to include a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, or a chelating agent. PH of borate, oxalate, carbonate, phosphate etc.
Those which are known to be added to a normal bleaching solution, such as a buffer, an alkylamine, and a polyethylene oxide, can be appropriately added.

Further, the fixing solution and the bleach-fixing solution include sulfites such as ammonium sulfite, potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite and the like, boric acid, borax, sodium hydroxide, potassium hydroxide. , Sodium carbonate, potassium carbonate,
A single or two or more pH buffers comprising various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained.

When processing is performed while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate or sulfite, or the bleach-fix. These salts may be added to the replenisher to replenish the treatment bath.

In order to increase the activity of the bleaching solution or bleach-fixing solution, air or oxygen may be blown in the bleach-fixing bath and in the bleach-fix replenisher storage tank if desired, or a suitable oxidizing agent, for example, Hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

The pH of the bleach-fixing solution preferably used in the present invention is from 3.0 to 3.0.
9.0 is preferred, and the range is more preferably 4.0 to 8.0. The bleach-fix processing time is 10 seconds or longer, preferably 20 seconds or longer. However, in order to achieve the effects of the present invention, the longer the time is, the longer the time is, for example, 50 seconds or more, the more remarkable the effects of the present invention become.

In the process of washing with water or a substitute for washing with water after bleach-fixing, silver may be recovered from a processing solution containing a soluble silver complex such as a fixing solution or a bleach-fix solution by a known method. For example, an electrolysis method (French Patent No. 2,299,667), a precipitation method (JP-A-52-73037, German Patent 2,331,220), an ion-exchange method (JP-A-51-17114, German Patent 2,548,237)
No.) and metal substitution method (UK Patent No. 1,353,805) can be effectively used.

After the color developing process using the color developing solution of the present invention, the bleach-fixing process may be followed by a stable process without washing, or a washing process followed by a stable process. In addition, when performing the stabilization treatment, an ion exchange resin, electrodialysis, or the like may be performed, and then the resultant may be used as a stabilizing solution. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. The following steps are included as typical specific examples of a preferable treatment method.

(1) Color development → bleach-fix → washing with water (2) Color development → bleach-fix → small amount of washing → washing (3) Color development → bleach-fix → washing → stable (4) Color development → bleach-fix → stable (5) Color developing → Bleaching and fixing → First stable → Second stable The color developing solution of the present invention is a color paper, a color film, a color positive film, a color positive paper, a color reversal film for slides, a color reversal film for movies, a color reversal film for TV, reversal. It can be applied to color photographic light-sensitive materials such as color paper.

The light-sensitive material processed by the color developing solution of the present invention has a silver chloride content of 90 mol% or more, more preferably 95 mol% or more,
Low replenishment and desilvering properties of the color developing solution are good, and processing stability is achieved. The crystals of silver halide grains are
Normal crystal, twin crystal or other, {100} face and {11}
Any ratio can be used for the 1｝ surface. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) may be used.

The silver halide grains are preferably substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, and an ammonia method.

Incidentally, since the particle size distribution of the monodispersed emulsion is almost normally distributed, the standard deviation can be easily obtained. From now on If you define the width (%) of the distribution by
Those having a monodispersity of 20% or less are preferred, and more preferably 10% or less. The particle size is the diameter in the case of spherical silver halide grains, and in the case of other than spheres, it is determined by converting into spheres of the same area.

The silver halide makes seed grains by an acidic method,
It may be grown by an ammonia method having a high growth rate and grown to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as primary sensitizers
Tin salts, thiourea dioxide, polyamines and the like; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-fluorothio-3-
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as, for example, ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these) Certain compounds act as sensitizers or fog inhibitors depending on the amount of the compounds, etc.) alone or in combination as appropriate (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a gold sensitizer). Chemical sensitization in combination with a selenium sensitizer).

The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during or after the ripening, at least one of a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and a mercapto group. One kind may be included.

The silver halide is optically sensitized by adding a sensitizing dye in an amount of 5.times.10.sup.- ⁸ to 3.times.10.sup.- ³ mol per mol of the silver halide in order to impart photosensitivity to a desired photosensitive wavelength region. Is also good. Various sensitizing dyes can be used,
Further, sensitizing dyes can be used alone or in combination of two or more.

The light-sensitive material to which the present invention can be applied includes a red light-sensitive silver halide emulsion layer, a blue light-sensitive silver halide emulsion layer, and a green light-sensitive silver halide emulsion layer each having a coupler, that is, a dye which reacts with an oxidized form of a color developing agent. A compound containing a compound capable of forming is preferred.

As the yellow coupler that can be used, a closed ketomethylene compound, an active site-o-aryl-substituted coupler, a so-called 2-equivalent coupler, an active site-o-acyl-substituted coupler, an active site hydantoin compound-substituted coupler, and an active site urazole compound-substituted Couplers and active site succinimide compound-substituted couplers, active site fluorine-substituted couplers. Active site chlorine or bromine substituted couplers, active site -o-sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of the yellow coupler that can be used include U.S. Pat.Nos. 2,875,057, 3,265,506, 3,408,194, and 3,551,155.
No. 3,582,322, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,
425,020, JP-B-51-10783, JP-A-47-26133,
48-73147, 51-102636, 50-6341, 50
-123342, 50-130442, 51-21827, 50-8
No. 7650, No. 52-82424, No. 52-115219, No. 58-95346
Nos. And the like can be mentioned.

Examples of magenta couplers that can be used include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow couplers. Specific examples of magenta couplers that can be used include U.S. Patent Nos. 2,600,788, 2,983,608,
No. 062,653, No. 3,127,269, No. 3,311,476, No.
No. 3,419,391, No. 3,519,429, No. 3,558,319, No. 3,582,322, No. 3,615,506, No. 3,834,908,
No. 3,891,445, West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2,408,665, No. 2,417,945, No. 2,41
No. 8,959, No. 2,424,467, JP-B-40-6031, JP
No. 51-20826, No. 52-58922, No. 49-129538, No. 49-
74027, 50-159336, 52-42121, 49-7402
No. 8. No. 50-60233, No. 51-26541, No. 53-55122,
Examples thereof include those described in Japanese Patent Application No. 55-110943. A particularly preferred magenta fogger is disclosed in JP-A-63-163, which is effective for preventing processing fluctuations and yellow stain after processing.
General formula [M-1] described in JP-A-106655 (pp. 510 to 518)
It is a magenta cabbler represented by.

Examples of usable cyan couplers include phenol-based and naphthol-based couplers.
These cyan couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow couplers. Specific examples of cyan couplers that can be used include U.S. Patent Nos. 2,369,929, 2,434,272, and 2,472.
No. 4,293, No. 2,521,908, No. 2,895,826, No. 3,0
No. 34,892, No. 3,311,476, No. 3,458,315, No. 3,
No. 476,563, No. 3,583,971, No. 3,591,383, No.
3,767,411, 3,772,002, 3,933,494, 4,004,929, West German Patent Application (OLS) 2,414,830,
No. 2,454,329, JP-A-48-5983, 51-26034,
No. 48-5055, No. 51-146827, No. 52-69624, No. 52
-90932, 58-95346, and JP-B-49-11572. Particularly preferred cyan couplers are represented by the general formulas [C-1] and [C-2] described in JP-A-63-106655 (pages 518 to 526) which are effective for preventing stain after treatment and fluctuations in treatment. Is a cyan coupler.

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

The amount of the coupler is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, more preferably 1 × 10 ⁻³ mol, per mol of silver.
^{-2 to} 5 × 10 ^-1 mol.

The silver halide color photographic light-sensitive material to which the present invention can be applied may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure Magazine No. 17643 Agents, plasticizers, wetting agents and the like can be used.

In the photosensitive material to which the present invention can be applied, hydrophilic colloids used for preparing an emulsion include gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, albumin, proteins such as casein, hydroxyethyl cellulose derivatives, Any of cellulose derivatives such as carboxymethylcellulose, starch derivatives, and single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

As a support of the photographic light-sensitive material to which the present invention can be applied,
Reflective supports and transparent supports such as baryta paper and polyethylene-coated paper can be mentioned, and these supports are appropriately selected according to the intended use of the photosensitive material.

In the light-sensitive material to which the present invention can be applied, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer are formed. Can be used in appropriate combination. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

In the present invention, the effects of the first and second objects of the present invention are favorably exhibited by using a nitrogen-containing heterocyclic mercapto compound in combination in the high silver chloride emulsion layer of the present invention,
It is also effective in preventing stain in the bleach-fix solution.

In the nitrogen-containing heterocyclic mercapto compound, the nitrogen-containing heterocycle is an imidaline ring, an imidazole ring, an imidazolone ring,
Pyrazoline ring, oxazoline ring, oxazole ring, oxazolone ring, thiazoline ring, thiazole ring, thiazolone ring, selenazoline ring, selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benzotriazole Ring, indazole ring, benzoxazole ring, benzothiazole ring, benzoselenazole ring, virazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, thiazine ring, tetrazine ring, quinazoline ring, phthalazine ring, polyazaindene ring ( For example, it is desirably selected from triazaindene ring, tetrazaindene ring, pentazaindene ring, etc.). Of these, particularly preferred nitrogen-containing heterocyclic mercapto compounds include oxazole rings, oxadiazole rings, thiadiazole rings,
A triazole ring, a tetrazole ring, a benzimidazole ring, a benzotriazole ring, a pyrimidine ring, a triazine ring, and a polyazaindene ring.

Hereinafter, specific examples of the nitrogen-containing heterocyclic mercapto compound useful in the present invention will be described.

The compounds described above were obtained from Journal of Chemical Society (J. Chem. Soc.) 49, 1948, 1927, and Journal of Organic Chemistry (J. Org. Chem.) 39, 2
469, 1965; JP-A-50-89034; JP-A-55-79436;
-102639, 55-59463, Annalen Hemy (A
nn. Chim.), 44-3, 1954, JP-B-40-28496, Chemical Berchte (Chem. Ber.) 20, 231, 1887, U.S. Patent
No. 3,259,976, Chemical and Pharmaceutical Bull
etin) (Tokyo) Volume 26, 314 (1978), Berichte der
Deutschen Hemischen Geels Draft (Be
richte der Deutscben Chemischen Gesellsdraft) 82,
121 (1948), U.S. Patent Nos. 2,843,491, 3,017,270,
UK Patent 940,169, Journal of American
The compound can be synthesized with reference to the method described in Chemical Society, 44, 1502-1510 and the like.

The nitrogen-containing heterocyclic mercapto compound (hereinafter, simply referred to as a mercapto compound) is described in, for example, JP-A-51-1071129.
Nos. 48-102621, 55-594463 and 59-124333
It is described in each gazette of the issue.

In the present invention, the mercapto compound is preferably added to two or more of the high silver chloride emulsion layers of the present invention.

The total amount of the mercapto compound used varies widely depending on the layer constitution of the silver halide photographic light-sensitive material, the type of the mercapto compound, the amount of silver halide, processing conditions, etc., and is generally from 10 ^-8 mol to 10 mol / m ^{2. -4} mol, preferably 10 ^-7 mol to 1
Although it is in the range of 0 to ⁵ mol, in the present invention, it is not limited to the total amount itself, but is defined by the degree of fog prevention of each emulsion layer and the magnitude of the effect of the mercapto compound between each layer.

〔Example〕

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

Reference Example 1 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a photosensitive material (color paper).

The average molecular weight of polyethylene coated paper is 10
0000, 200 parts by weight of polyethylene of density 0.95 and average molecular weight 2
000, a mixture of 20 parts by weight of polyethylene having a density of 0.80, 6.8% by weight of anatase type titanium oxide was added, and a coating layer having a thickness of 0.035 mm was formed on the surface of a high-quality paper having a weight of 170 g / m ² by an extrusion coating method. The back surface was provided with a coating layer having a thickness of 0.04 mm using only polyethylene. After pretreatment by corona discharge was performed on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion having a silver chloride content of 99.0 mol%, which emulsion contains 350 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye 200 mg of 2,5-di-t-butylhydroquinone sensitized using 2.5 × 10 ⁻⁴ mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate
/ m ² and the following yellow coupler Y as yellow coupler
R-1 containing 2 × 10 ^-1 mol per mol of silver halide;
It is applied so that the silver amount is 300 mg / m ² .

Second layer: 300 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole and 2-
A mixture of (2-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole 200 mg /
The gelatin layer containing m ² is coated so as to have a gelatin of 1900 mg / m ² .

Third layer: A green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion having a silver chloride content of 99.5 mol%, which emulsion contains 450 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye The following magenta coupler MR-1 was sensitized using 2.5 × 10 ^-4 mol, and dissolved and dissolved in a solvent in which dibutyl phthalate and tricresyl phosphate were mixed at a ratio of 2: 1. It is coated so as to contain × 10 ^-1 mol and to have a silver amount of 280 mg / m ² . Here, 0.3 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was contained as an antioxidant per 1 mol of the coupler.

Fourth layer: 30 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole as an ultraviolet absorber , 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2
-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5'-chlorobenzotriazole and 2- (2'-hydroxy-3 ', 5'-tert-butylphenyl) -5 A mixture of chlorobenzotriazoles (2: 1.5:
1.5: 2) the amount of gelatin 1 at 500 mg / m ² gelatin layer containing
It is coated to be 900 mg / m ^2.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion having a silver chloride content of 99 mol%. The emulsion contains 500 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye 2,5-Di-t-butylhydroquinone 150 mg / m ² sensitized with 2.5 × 10 ^-5 mol and dispersed in dibutyl phthalate and the following cyan coupler CR-1 as a cyan coupler were used as silver halide. It is coated so as to contain 3.5 × 10 ^-1 mol per mol and to have a silver amount of 280 mg / m ² .

Sixth layer: The gelatin layer is coated so that the amount of gelatin is 900 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized, and 4-hydroxy-6-methyl-
It contained 1,3,3a, 7-tetrazaindene, bis (vinylsulfonylmethyl) ether as a hardening agent and saponin as a coating aid.

After the printing of the photosensitive material described above, the photosensitive material was subjected to a running process by an automatic developing machine using the following processing steps and the following processing solutions.

Processing Steps (1) Color development 33 ° C for 3 minutes 30 seconds (2) Bleaching and fixing 35 ° C for 1 minute (3) Rinsing alternative stability 30 ° C to 35 ° C 2 minutes (4) Drying 60 ° C to 85 ° C About 2 minutes Used The composition of the treatment liquid is as follows.

Color developing tank solution Potassium bromide 0.6 g Potassium chloride 2.5 g Potassium sulfite (50% solution) 1.0 m Color developing agent (3-methyl-4-amino-N-ethyl-
N- (β-methanesulfonamidoethyl) -aniline sulfate 5.4 g Preservative (described in Table 1) 5.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Sodium diethylenetriaminepentaacetate 5.0 g Finished with water to 1 Potassium hydroxide or sulfuric acid At pH 10.15
Was adjusted.

Replenisher for color development Potassium bromide 0.7 g Potassium chloride 2.5 g Potassium sulfite (50% solution) 1.0 m Color developing agent (3-methyl-4-amino-N-ethyl-)
N- (β-methanesulfonamidoethyl) -aniline sulfate 7.5 g Preservative (described in Table 1) 7.0 g Triethanolamine 10.0 g Potassium carbonate 30 g Diethylenetriaminepentaacetic acid 5.0 g Finished with water to 1 with potassium hydroxide or sulfuric acid pH10.40
Was adjusted.

Bleach-fixing tank solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0m Ammonium sulfite (40% solution) 20m Adjust pH to 5.50 with ammonia water or glacial acetic acid Together with water to bring the total to 1.

Replenisher for bleach-fix Ethylenediaminetetraacetic acid ferric ammonium dihydrate 70.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 120 m Ammonium sulfite (40% solution) 20 m Adjust pH to 5.40 with aqueous ammonia or glacial acetic acid Add water to bring the total volume to 1.

Rinse tank solution instead of water washing Sodium dichloroisocyanurate 0.1 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Benzotriazole 0.1 g Ethylene glycol 1.0 g 2-octyl-4-isothiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) and 1 3.0 g BiC _{3 (45%} aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g of ammonia water (ammonium 25% aqueous hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g water, ammonia water and sulfuric acid To pH 7.0.

The running process is performed by filling the above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution in an automatic developing machine, and processing the color paper sample at intervals of 3 minutes. And a water-washing alternative stable replenisher were replenished through a metering pump.

The replenishment rate of the color development tank is color paper 1 m ² per 160 m, the replenishment rate of the bleach-fixing tank color paper
The bleach-fix replenisher per 1 m ² was as shown in Table 1, and the replenishment to the stabilization tank was performed by replenishing 250 m of a stabilizing replenisher instead of washing.

The stabilizing bath of the automatic developing machine is a stabilizing bath which becomes the first to third baths in the flow direction of the photosensitive material, and replenishment is carried out from the last bath. The overflow liquid was further allowed to flow into the preceding tank to form a multi-tank countercurrent system.

When the amount of the bleach-fix replenisher replenished in the bleach-fix tank becomes three times the capacity of the bleach-fix tank, pass the wedge-exposed check sample through the PDA-65 (manufactured by Konica Corporation). The concentration was measured. The results are shown in Table 1.

As is clear from Table 1, when the color development process is performed using the preservative example of the present invention, and the replenishment amount of the bleach-fix solution is the replenishment amount of the present invention, the generation of stain is effectively suppressed. It can be seen that the use of a preservative, hydroxylamine sulfate, D-glucosamine hydrochloride or glucose, which is a preservative outside the present invention, has almost no stain prevention effect as seen in the present invention.

Further, in Sample Nos. 1-7 and 1-8, the potassium chloride in the color developer after the completion of the running process was adjusted as shown in Table 1A, and the replenishment amount of the color developer was changed as shown in Table 1A. Except for the above, the same processing was performed, and the lowest concentration of each sample was measured. The results are shown in Table 1A.

As is clear from Table 1A, the chloride concentration in the color developing solution needs to be 3.0 × 10 ^-2 mol / or more, and the replenishment amount of the color developing solution is 180 m or less, and particularly 120 m / m ² of the photosensitive material.
The following shows that the effect of the present invention is great.

Reference Example 2 The color developing solution and the bleach-fix solution (1-1 to 1-24) after the running process used in Example 1 were applied at 50 ° C. at an opening area (air contact area per bleach-fix solution) of 15 cm ² /. The color developer was observed for the number of days required for tar generation, and for the bleach-fix solution, the number of days required for sulfuration was observed.
Table 2 shows the results.

As is apparent from Table 2, when a preservative other than the present invention is used in the color developing solution, tar is easily generated, and sulfuration of the bleach-fix solution uses a preservative other than the present invention in the same manner as the color developing solution. It can be seen that the use of the preservative of the present invention has improved the generation of tar in the color developing solution and the storage stability of the bleach-fixing solution. It is also apparent that the effect of the present invention is more remarkable when the replenishment amount of the bleach-fix solution is reduced by using the preservative of the present invention.

Reference Example 3 The silver halide composition of the silver halide color photographic light-sensitive material was set to the composition shown in Table 3, and the preservative of the color developing solution was changed to the exemplified compound A-1 of the hydroxylamine derivative represented by the general formula [I]. Other than that, the same processing as in Reference Example 1 was performed, and the amount of residual silver after the processing was measured. Table 3 shows the results.

As is clear from Table 3, it can be seen that the higher the silver chloride content, the smaller the replenishment amount of the bleach-fixing solution, the smaller the residual silver content especially at 90 mol% or more. From these results, it can be said that the silver halide color photographic light-sensitive material containing high silver chloride is excellent in desilvering and is suitable for low replenishment of the bleach-fix solution.

Reference Example 4 Using the silver halide color photographic light-sensitive material of Reference Example 1,
To each of the color developing tank solution and the color developing replenisher, benzyl alcohol was added at a rate of 1.5 m / l, and as a preservative, exemplified compounds A-1, A-18 or hydroxylamine of a hydroxylamine derivative represented by the general formula [I] were added. The same experiment as in Reference Example 1 was performed except that the sulfate was used.
However, the replenishment rate of the bleach-fix solution was 80 m /. After the running treatment, the bleach-fixing time was changed as shown in Table 4, and the same evaluation as in Reference Example 1 was performed. Table 4 shows the results.

As is clear from Table 4, when the hydroxylamine derivative of the present invention is used in a color developing solution, surprisingly, even when the bleach-fixing processing time is lengthened, stain is hardly generated, and the effect is remarkably exhibited. .

Reference Example 5 A magenta coupler was prepared by using M'-1, M'-2, M'-4, M'-21, M'-37 described in JP-A-63-106655.
M'-62 and M'-63 were replaced by cyan couplers as disclosed in
No. 6655, C'-2, C'-27, C'-32, C '
-33, C'-34, C'-36, C'-37, C'-38, C '
-39, C'-53, C "-2, C" -8, and C "-9 except that the same silver halide color photographic light-sensitive material as in Reference Example 1 was used, and the same experiment as in Reference Example 4 was performed. As a result, the magenta stain was improved by 0.01 to 0.03 and the cyan stain was improved by 0.02 to 0.04.The effect was particularly significant as the bleach-fixing time was longer (60 seconds or more).

Example 1 In each emulsion layer of a silver halide color photographic light-sensitive material, the exemplified compounds (I-24), (I-41) and
The same silver halide color photographic light-sensitive material as in Reference Example 1 was used except that (I-60), (I-66), (I-79) and (I-84) were each added at 0.12 mg / m ² , When an experiment similar to that in Example 4 was performed, it was effective in suppressing the stains of yellow, magenta, and cyan similarly to Reference Example 5, and each of them had an effect of 0.1%.
01-0.03 stain concentration decreased. In particular, as in Reference Example 5, the effect was remarkable as the bleach-fixing time became longer.

〔The invention's effect〕

According to the present invention, tar and stain generated when the bleach-fixing process is replenished at a low level (due to a decrease in the concentration of sulfurous acid) and a decrease in desilvering property (increase in the mixing ratio of the color developing solution into the bleach-fixing solution) Is improved.

Continuation of front page (56) References JP-A-62-246049 (JP, A) JP-A-62-249152 (JP, A) JP-A-62-196662 (JP, A) JP-A-62-258451 (JP) JP-A-60-23857 (JP, A) JP-A-62-253142 (JP, A) JP-A-63-24255 (JP, A) WO 87/6026 (WO, A1)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material comprising, on a support, at least one silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more and a nitrogen-containing heterocyclic mercapto compound. When the material is subjected to bleach-fixing processing after color development processing, the color developing solution contains a hydroxylamine derivative represented by the following general formula [I] and 3.0 × 1
0 to ² mol / or more chloride, and the replenishment amount of the color developing solution is 30 to 180 m per 1 m ^{2 of the} light-sensitive material, and the replenishment amount of the bleach-fix solution is 100 m or less per 1 m ^{2 of the} light-sensitive material. A method for processing a silver halide color photographic light-sensitive material, characterized in that: [Wherein, R ¹ and R ² each represent an alkyl group or a hydrogen atom. However, both R ¹ and R ² are not hydrogen atoms at the same time. R ¹ and R ² may form a ring. ]