JP2652677B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and particularly to a rapid silver halide color having excellent desilvering water, low fog and high color density. The present invention relates to a method for developing a photographic light-sensitive material.

(Prior art) The processing of silver halide color photographic light-sensitive material basically consists of two steps of color development (in the case of a color reversal material, the first black-and-white development before it) and desilvering. Consists of a bleaching and fixing step or a single-bath bleach-fixing step used together or alone. If necessary, other additional processing steps, such as washing, stop processing, stabilizing processing, and pre-processing for promoting development, are added.

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. In this process, halogen ions generated by the decomposition of silver halide are eluted and accumulated in the developer. On the other hand, the color developing agent is consumed by the reaction with the coupler described above. Further, other components are carried out by being held in the photographic light-sensitive material, and the concentration of the components in the developer decreases. Therefore, in a developing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in the development finish characteristics due to a change in the component concentration. It is necessary to keep. As a method for this, a method of replenishing a replenisher for compensating for the deficient component and diluting the increased component is usually employed. However, when continuous processing was carried out while replenishing using a high silver chloride emulsion, it was found that the photographic characteristics varied considerably, such as an increase in fog and a decrease in the maximum density.

On the other hand, a number of techniques have been conventionally studied to perform rapid processing. Among them, JP-A-61-70552 and International Publication (PCT application) WO 87/04534 aim to reduce the accumulation of bromine ions, which are strong development inhibitors, and to increase the speed.
A method using a silver halide photographic light-sensitive material having a high silver chloride content has been proposed.

JP-A-63-106655 discloses that a silver halide color photographic material having a silver halide emulsion layer having a high silver chloride content is developed with a color developing solution containing a hydroxylamine compound and a chloride at a predetermined concentration or more. A method of processing is disclosed.

JP-A-62-250438 discloses that a red-sensitive emulsion layer contains silver halide grains having a silver chloride content of 80 mol% or more and contains a specific hardener and a sensitizing dye. A silver halide photographic light-sensitive material is disclosed.

(Problems to be Solved by the Invention) If the bleaching of the image silver formed by color development is incomplete, the color of a color photograph (particularly noticeable in the yellow portion) becomes dark due to the formation of silver sulfide and the like. Therefore, improvement of the desilvering property is an important issue, but the method described in JP-A-63-106655, which is high in silver chloride, is treated with a coupler developer containing a chloride having a small inhibitory effect on stabilized color development. It was not sufficient in terms of desilvering. In this case, even if a bleaching accelerator is added, poor desilvering is hardly improved, which can be said to be a phenomenon peculiar to high silver chloride.

Further, in the methods described in JP-A-61-70552 and WO 87/04534, if the replenishment rate of the developing solution is reduced without impairing the rapidity, the photographic characteristics significantly change during continuous processing, It has been found that new problems such as the generation of suspended matter occur. This suspended matter is mainly composed of sludge attributed to the eluted Ag ⁺ , but cannot be prevented by adding a chelating agent to the developer.

Further, according to these methods, fog which is considered to be caused by development fog or bleaching fog is apt to occur during continuous processing, so that the minimum density increases, the maximum density decreases, and the photographic characteristics fluctuate. Elimination of points is required.

Further, even in the processing method of a silver halide photographic light-sensitive material described in JP-A-62-250438, a sufficient effect was not obtained in terms of the desilvering performance and the fluctuation of photographic characteristics described above.

Accordingly, a first object of the present invention is to provide a processing method in which a silver halide photographic light-sensitive material is processed with a color developer in which desilvering properties are improved without lowering color developing properties.

A second object of the present invention is to provide a processing method in which a high silver chloride photographic material is continuously processed with a color developer without causing fog in rapid processing and preventing a decrease in the maximum density.

Further, a third object of the present invention is to provide a processing method which uses a high silver chloride photographic light-sensitive material and which does not impair the rapidity of processing and in which the generation of suspended matter (sludge) in a developing solution is prevented. It is to be.

(Means for Solving the Problems) An object of the present invention is to provide a method for continuously processing a silver halide color photographic material with a color developer containing at least one aromatic primary amine color developing agent. has a monodispersed silver halide emulsion containing silver chloride 80 mol% or more in at least one layer, the amount of coated silver per 1 m ² 0.8
The silver halide color photographic light-sensitive material is 0 g / m ² or less,
Silver halide characterized by being processed using a color developer having a chloride ion concentration of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / and a sulfite ion concentration of 0 to 3 × 10 ^-3 mol / This was achieved by a processing method for color photographic light-sensitive materials.

In at least one layer of the silver halide color photographic light-sensitive material used in the present invention, silver halide is 80% or more.
Mol% or more, preferably 95 mol% or more, more preferably
Contains 96-99.5 mol% silver chloride. If the silver chloride content is less than 80 mol%, a sufficient color density cannot be obtained, and the effect of the present invention is insufficient.

The silver halide emulsion containing at least 80 mol% of silver chloride used in the present invention is a monodispersed emulsion.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution in which the variation coefficient (S /) relating to the grain size of silver halide grains is 0.15 or more. Here, the average particle size, S, is the standard deviation related to the particle size.

That is, when the particle size of each emulsion particle is ri and the number is ni, the average particle size is And its standard deviation S is Is defined as

The individual grain size in the present invention means a silver halide emulsion.
`` The Theory of the Photographic Proc '' by THJames et al.
ess ", 3rd edition, pp. 36-43, published by Macmillan (1966)
And a projected area equivalent diameter corresponding to an area projected when microphotographed by a method well known in the art (usually electron micrographing) as described in (1). Here, the projected equivalent diameter of the silver halide grain is defined by the diameter of a circle equal to the projected area of the silver halide grain as described in the above-mentioned book. Therefore, even when the shape of silver halide grains is other than spherical (for example, cubic, octahedral, tetrahedral, flat, potato, etc.), the average grain size and its deviation S can be determined as described above.

The coefficient of variation relating to the grain size of the silver halide grains is 0.15 or less, preferably 0.10 or less. If the coefficient of variation is larger than that of the present invention, the effects of the present invention cannot be obtained in terms of desilvering properties and photographic characteristics.

The amount of silver coated in the silver halide color photographic light-sensitive material used in the present invention is usually 0.80 g / m ² or less, more preferably 0.75 g / m ² or less, per 1 m ^{2 of the} light-sensitive material. The lower limit is appropriately determined, but is preferably 0.40 g / m ² or more. If the amount of silver applied is too large, fogging is likely to occur, and poor silver removal or silver sludge may occur.

The light-sensitive material of the present invention preferably has a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. An intermediate layer is preferably provided between these photosensitive layers. An undercoat layer may be provided on the support, and a protective layer may be provided on the uppermost layer.

In the present invention, the chloride ion concentration in the color developer is usually from 3.5 to 10 ^{-2 to} 1.5 to 10 ^-1 mol /, preferably from 4 to 10.
× 10 ^{-2 to} 1.0 × 10 ^-1 mol /. Chloride ion concentration
If it exceeds 1.5 × 10 ⁻¹ mol / mol, the effect of the present invention is insufficient, and the maximum concentration is undesirably reduced. If it is less than 3.5 × 10 ^-2 mol / m, fogging tends to occur, and the desilvering performance is inferior.

The chloride ion concentration may be adjusted by adding a chloride in the replenisher or may be added to the tank from the beginning. In addition, it may be eluted from the photosensitive material during the continuous processing to have the above concentration. In this case, it can be adjusted by reducing the replenishment amount of the color developer. Preferred as such chlorides are sodium chloride, potassium chloride, lithium chloride, magnesium chloride and the like.

In the present invention, the color developer does not substantially contain sulfite ions. Here, “substantially not containing” means that the sulfite ion concentration is 3 × 10 ⁻³ mol / or less,
It is preferably from 0 to 1.5 × 10 ⁻³ mol /, and most preferably it does not contain any sulfite ions.

Replenishing amount of the color developing solution according to the present invention is a silver halide color photographic light-sensitive material 1 m ² per, 120 ml or less, for example 30 to 12
Can be reduced to 0 ml.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. It is particularly preferable to apply to paper among the above.

In the present invention, the reason why the problems of poor desilvering, fogging, reduction of the maximum density and generation of suspended matter in the developing solution are not yet clear, but a relatively large size which is liable to fog or poor desilvering is partly unknown. Since the development is carried out in the presence of high chloride ions in addition to the reduced presence of grains, the grain size is controlled to be relatively small by reducing the solubility of the surface of the silver halide grains. Is estimated to have improved.

In the present invention, it is necessary that the color developer does not substantially contain sulfite ions. However, in order to suppress the deterioration of the developer, the developer is not used for a long time, and the color developer is floated in order to suppress the influence of air oxidation. It is possible to use a physical means such as using a pig or reducing the opening degree of the developing tank, a chemical means such as suppressing the temperature of the developing solution, or adding an organic preservative. Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines, etc. It is an effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-1888619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
Nos. 6559, 61-170756, 61-188742, 61-1887
No. 41, U.S. Pat.Nos. 3,615,503 and 2,494,903,
52-143020 and JP-B-48-30496.

With respect to the preferred organic preservatives, general formulas and specific compounds are shown below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / ~ 0.5 mol /, preferably 0.03 mol / ~
It is desirable to add so as to have a concentration of 0.1 mol /.

Particularly, addition of a hydroxylamine derivative and / or a hydrazine derivative is preferable.

The hydroxylamine derivative is preferably represented by the following general formula (I).

General formula (I) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R ¹¹ and R ¹² are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring and is constituted by a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

R ¹¹ and R ¹² are preferably alkyl or alkenyl groups, and preferably have 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the nitrogen-containing hetero ring formed by linking R ¹¹ and R ¹² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholinyl group, an indolinyl group, and a benzotriazole group.

Preferred substituents of R ¹¹ and R ¹² are hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (II) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. The heterocyclic group is a 5- to 6-page ring,
It is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. X ³¹ is -CO-, -SO ₂
-Or And n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In the general formula (II), R ³¹ , R ³² and R ³³ represent a hydrogen atom or C ₁ -C
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (II), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Here, preferable substituents of the alkyl group include a carboxysyl group, a sulfo group, a nitro group, an amino group and a phosphono group. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

(Compound example) _{II-2 NH 2 NHCH 2 4} SO 3 H II-3 NH 2 NHCH 2 2 OH _{II-6 NH 2 NHCOCH 3 II} -7 NH 2 NHCOOC 2 H 5 II-10 NH ₂ NHCONH ₂ II−12 NH ₂ NHSO ₃ H II-14 NH ₂ NHCOCONHNH ₂ II-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H II-18 NH ₂ NHCH ₂ CH ₂ COOH Use of the compound represented by the general formula (I) or (II) in combination with the amine represented by the following general formula (III) or (IV) can improve the stability of a color developer. Is more preferable from the viewpoint of improving stability during continuous processing.

General formula (III) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R
⁷³ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferred. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

(Compound example) III-1 NCH ₂ CH ₂ OH) ₃ III-2 H ₂ NCH ₂ CH ₂ OH III-3 HNCH ₂ CH ₂ OH) ₂ III-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ III-11 HNCH ₂ COOH) ₂ III−13 H ₂ NCH ₂ CH ₂ SO ₂ NH _{2 III-15 H 2 N-CCH} 2 OH) 2 In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other.

Among the general formulas (IV), particularly preferred are the compounds represented by the general formulas (IV-a) and (IV-b).

In the formula, X ¹ represents N or CH. R ¹ and R ² are the same as defined in the general formula (V), and R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (IV-a), X ¹ is preferably N. The number of carbon atoms of R ¹ , R ² and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (V).

In the general formula (IV-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (IV-a) and (IV-b), the compound represented by the general formula (IV-a) is particularly preferable.

The above organic preservative can be obtained as a commercial product, but can also be synthesized by the methods described in Japanese Patent Application Nos. 62-124038 and 62-24374.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N -(Β-hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N (β
-Methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per developing solution.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N'N, N'-tetramethylenephosphonic acid, 1,3 −
Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2
-Diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetate, catechol-3,4,6-
Trisulfonic acid, catechol-3,5-disulfonic acid, 5
-Sulfosalicylic acid, 4-sulfosalicylic acid, These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-90190, and thioether compounds represented by U.S. Pat.No. 3,813,247, and p-type compounds disclosed in JP-A Nos. 52-49829 and 50-15554. -Phenylenediamine compounds, JP-A-50-
137726, JP-B-44-30074, quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, p-aminophenols described in U.S. Patent Nos. 2,610,122 and 4,199,462, U.S.A. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Shoko 4
1-111431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
532,501 polyalkylene oxide represented, etc.
In addition, 1-phenylene-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means per color developer
2.0 ml or less, more preferably not containing at all. When the content is not substantially contained, the fluctuation of photographic characteristics during continuous processing is small, and more preferable results are obtained.

In the present invention, an optional antifoggant can be added as needed. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. In particular, in the present invention, bromine ions are added in an amount of 4 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol.
The inclusion is a more preferred embodiment for achieving the effects of the present invention. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.

The color developer used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfostinbene compounds are preferred. The addition amount is 0 to 10 g /, preferably 0.1 to 6 g /.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

In the present invention, desilvering is performed after color development.
The desilvering step generally comprises a bleaching step and a fixing step, but it is particularly preferred that the steps are performed simultaneously.

The bleaching solution or bleach-fixing solution used in the present invention includes bromide (for example, potassium bromide, sodium bromide, ammonium bromide) or chloride (for example, potassium chloride,
A rehalogenating agent such as sodium chloride, ammonium chloride) or iodide (eg, ammonium iodide) can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
1 with pH buffering capacity such as sodium citrate, tartaric acid
More than one kind of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; A thioether compound such as bisthioglycolic acid, 3,6-dithia-1,8-octanediol and a silver halide dissolving agent for an aqueous solution such as thioureas, used alone or in combination of two or more. be able to. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
In the range of ~ 1.0 mole.

In the present invention, the pH range of the bleach-fixing solution or the fixing solution is as follows:
3 to 10 are preferable, and 5 to 9 are particularly preferable. pH
If the content is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco formation of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stains are easily generated.

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

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

In the present invention, the bleach-fixing solution or the fixing solution may be a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. ) And metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately
The content is preferably 0.02 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol.

As a preservative, sulfite is generally added,
In addition, ascorbic acid, carbonyl bisulfite adducts, sulfinic acids, carbonyl compounds, sulfinic acids, and the like may be added.

Further, a buffer, an optical brightener, a chelating agent, a fungicide, and the like may be added as necessary.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering at the time of fixing or bleach-fixing.

The amount of washing water in the washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, and the washing step.
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture and
Terevision Engineers), Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calciur and magnesium described in Japanese Patent Application No. 131632/1986 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanate, and other benzotriazoles, etc. It is also possible to use the disinfectant described in "Sterilization, disinfection and antifungal technology of microorganisms" edited by the Sanitary Technology Association, and "Encyclopedia of antifungal and antifungal agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the washing with water. In such a stabilizing treatment, JP-A-57-8543 and JP-A-58-14834.
No. 59-184343, No. 60-220345, No. 60-238832
No. 60-239784, No. 60-239749, No. 61-4054,
The known methods described in JP-A-61-118749 and the like can all be used. In particular, 1-hydroxyethylidene-1,1-
A stable bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, after the water washing treatment, a stabilization treatment may be further performed, and examples thereof include a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography. .

The processing time of the present invention is defined as the time from the time when the photosensitive material comes into contact with the color developer to the time when it leaves the final bath (usually a washing or stabilizing bath). The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 4 minutes or less.

Next, the silver halide color photographic light-sensitive material used in the present invention will be described in detail.

The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. This may increase the amount of light absorption in terms of photosensitivity, enhance the adsorption of spectral sensitizing dyes, or reduce the desensitization due to spectral sensitizing dyes, and there are many useful points.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have a phase different from the inside and the surface layer, a multiphase structure having a bonding structure, or a whole grain. It may consist of a homogeneous phase. They may be mixed.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those having a regular crystal form such as tetradecahedron, spherical,
It may be a material having an irregular crystal such as a plate, a material having a crystal defect such as a twin plane, or a compound thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is described, for example, in Research Disclosure (RD), No. 17643 (1978).
December), p. 22-23, "1. Emulsion prepara
and types can be prepared using the methods described in "

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gatoff, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

As long as the crystal structure is uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide, such as, for example, rhodan silver or lead oxide.

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

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and are shown in the relevant places in the following table.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
No. 1,476,760 and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619, 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630,
No. 4,540,654 are particularly preferable.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, EP 161,626A and the like.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,367 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
Nos. 34, 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
And DIR redox compound releasing couplers described in, for example, JP-A-185950, and couplers that release dyes that recolor after release as described in EP 173,302A.

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

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

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

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

Next, preferred embodiments of the present invention will be described below.

(1) The processing method according to claim 1, wherein the color developer has a sulfite ion concentration of 3 × 10 ^-3 mol / or less.

(2) A processing step in which bleach-fixing processing is performed after a color development step, followed by washing and / or stabilization processing, wherein the total processing time is 4 minutes 30 seconds or less. For processing silver halide color photographic light-sensitive materials.

(Effect of the Invention) According to the photographic processing method of the present invention, the desilvering property can be improved upon continuous processing of a high silver chloride photographic material with a color developer. According to the method of the present invention, it is possible to prevent a decrease in the maximum density without causing fog in the element processing. According to the photographic processing method of the present invention, it is possible to significantly reduce the replenishment amount of the color developer without impairing the processing speed, and to prevent the generation of suspended solids and prevent the fluctuation of photographic characteristics during continuous processing. Thus, there is an excellent effect that a high-quality photographic image having stable development finish characteristics can be formed. The method of the present invention meets the objectives of saving resources and reducing pollution, and is suitable for a development treatment, such as a minilab, which is particularly restricted in discharging waste liquid.

(Examples) Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper A having the following layer constitution was produced on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsion 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g, 27.2 cc of ethyl acetate and a solvent (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

Hereinafter, magenta, cyan, and emulsions for the intermediate layer were prepared according to this method.

 The compounds using the respective emulsions are shown below.

(Solv-2) solvent O = PO-C ₈ H ₁₇ ) ₃ (Solv-3) solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The following dyes were added to the emulsion layer to prevent irradiation.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Next, a method for preparing the emulsions of Tables 1-A to 1-G used in this example will be described.

Blue-sensitive emulsion (in the case of Table 1 Sample 1-G) (1 liquid) H ₂ O 1000 cc NaCl 5.5g gelatin 32 g (2 solution) sulfuric acid (1N) 24 cc (3 solution) the following compound A (1%) 3 cc (4 solution) NaCl 1.7g H ₂ O were added 200 cc (5 solution) AgNO ₃ 5 g H ₂ O were added 200 cc (6 _{solution) NaCl 41.3g K 2 IrCl 6 (} 0.001%) 0.5cc H 2 O were added 600 cc (7 solution) AgNO ₃ 120 g H ₂ O were added 600 cc (1 liquid) was heated to 76 ° C., was added (2 solution) and (3 solution).

Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 10 minutes.

After another 10 minutes, (Sixth solution) and (Sixth solution) were simultaneously added for 35 minutes. Five minutes after the addition, the temperature was lowered and desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodispersed cubic silver chloride emulsion having an average particle size of 1.1 μm and a coefficient of variation (standard deviation divided by average particle size: s / d) of 0.10.

To 1.0 kg of this emulsion was added a spectral sensitizing dye for blue (S-1).
26 cc of a 0.6% solution was added, and a 0.05 μg AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% to the host AgCl emulsion, followed by mixing and ripening at 58 ° C. for 10 minutes. Thereafter, sodium thiosulfate was added, the chemical sensitization was optimally performed, and a stabilizer (Stb-1) was added at 10 ^-4 mol / mol Ag.

(For Table 1 Sample 1-G) the green-sensitive emulsion (8 _{fluid) H 2 O 1000 ml NaCl 3.3} g Gelatin 32 g (9 solution) sulfuric acid (1N) 24 ml (10 Solution) Compound A (1%) 3 ml (11 fluid) NaCl 11.00g H ₂ O were added 200 ml (12 fluid) AgNO ₃ 32.00g H ₂ O were added 200 ml (13 _{fluid) NaCl 44.00g K 2 IrCl 6 (} 0.001%) 2.3 ml H ₂ O was added and 560 ml (solution 14). AgNO ₃ 128 g H ₂ O was added, and 560 ml (solution 8) was heated to 52 ° C., and (solution 9) and (solution 10) were added. Thereafter, (solution 11) and (solution 12) were added simultaneously for 14 minutes. After another 10 minutes, (solution 13) and (solution 14) were added simultaneously for 15 minutes.

A sensitizing dye (S-2) was added to this emulsion in an amount of 1 mol of silver halide.
4 × 10 ^-4 mol and 8 × 10 ^-5 mol of (S-3) were added per 10 minutes, and then the following (liquid 15) was added over 10 minutes. After 5 minutes from the addition, the temperature was lowered to desalinate.

Add water and disperse gelatin, adjust pH to 6.2, (15 solutions) KBr 5.60 g H ₂ O, 280 ml Add sodium thiosulfate at 58 ° C, perform optimal chemical sensitization, average particle size A monodisperse cubic silver chloride emulsion having a coefficient of variation (standard deviation divided by average grain size; s / d) of 0.40 μm was obtained.

Further, (Stb-1) was used as a stabilizer in an amount of 1 mol of silver halide.
5 × 10 ^-4 mol / mol.

The red-sensitive emulsion was exactly the same as the green-sensitive emulsion except that the sensitizing dye used was changed to (S-4) and the amount added was 1.5 × 10 ^-4 mol per mol of silver halide. Was prepared.

Sample 1-E blue-sensitive layer Emulsion (1 _{liquid) H 2 O 1800 ml NaCl 48} g gelatin _{32 g K 2 IrCl 6 (0.001} %) 0.5cc (2 solution) sulfuric acid (1N) 24 cc (3 solution) AgNO ₃ 125 g H ₂ O was added, 800 ml (1 solution) was heated to 80 ° C., and (2 solution) was added. Then (3 solutions) was added simultaneously for 80 minutes. End of addition 5
After a minute, the temperature was lowered to desalinate.

Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a high silver chloride emulsion having an average particle size of 1.1 μm and a coefficient of variation of 0.20.

0.6% of blue spectral sensitizing dye (S-1) was added to 1 kg of this emulsion.
26 cc of the solution was added, and a 0.05 μg AgBr ultrafine grain emulsion was further added at a ratio of 0.5 mol% to the host AgCl emulsion, followed by mixing and ripening at 58 ° C. for 10 minutes. Thereafter, sodium thiosulfate was added, and the chemical sensitization was optimally performed, and the stabilizer (Stb-
1) was added at 10 ^-4 mol / mol Ag.

Sample 1-E green-sensitive layer Emulsion (4 _{solution) H 2 O 1700 ml NaCl 58} g K 2 IrCl 6 (0.001%) 2.3ml gelatin 40 g (5 solution) sulfuric acid (1N) 24 ml (6 solution) AgNO ₃ 160 g H ₂ O was added, 800 ml (4 solutions) was heated to 60 ° C. and (5 solutions) was added. Then (Six liquids) was added simultaneously, spending 60 minutes.

A sensitizing dye (S-2) was added to this emulsion in an amount of 4 × 10 ⁻⁴ mol per mol of silver halide, and (S-3) was added in an amount of 8 × 10 ⁻⁵ mol per mol. 5 minutes after the addition, the temperature was lowered to desalinate.

Add water and disperse gelatin, adjust the pH to 6.2, (15 solution) KBr 5.60 g H ₂ O, add 280 ml at 58 ° C, add sodium thiosulfate, perform optimal chemical sensitization, average particle size A high silver chloride emulsion having a coefficient of variation (standard deviation divided by average grain size; s / d) of 0.20 was obtained.

Further, (Stb-1) was used as a stabilizer in an amount of 1 mol of silver halide.
5 × 10 ^-4 mol / mol.

The red-sensitive emulsion was prepared in exactly the same manner as in the preparation of the green-sensitive emulsion, except that the sensitizing dye used was changed to (S-4) and the addition amount was 1.5 × 10 ^-4 mol per mol of silver halide. Prepared.

Next, 1-B, 1-D and 1-F were prepared by changing the chemical amount, temperature and addition time according to the emulsion preparation method of 1-G. Further, 1-A and 1-C were prepared according to the emulsion preparation method of 1-E.

 Next, the compounds used are shown.

(Layer Configuration) The composition of each layer in this sample (multilayer color photographic paper) is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated amount in terms of silver. However, each sample was prepared by changing the silver halide composition as shown in Table 1.

Support Polyethylene laminated paper (the first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)) First layer (blue sensitive layer) Silver halide emulsion 0.25 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.15 Gelatin 1.24 Magenta coupler (ExM) 0.60 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.62 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red-sensitive layer) Silver halide emulsion 0.20 Gelatin 1.34 Cyan coupler (Blend of ExC1 and C2,1: 1) 0.34 Color image stability Agent (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 6th layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.21 Solvent (Solv-3) 0.08 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification)
17%) 0.17 Liquid paraffin 0.03 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a hardening agent for each layer.

Each of the above photosensitive materials was subjected to wedge-shaped exposure at 250 CMS, and processed in the following processing steps.

In had the following composition processing steps Temperature Time Color development 37 ° C. 45 seconds blix 35 ° C. 45 sec Rinse 35 ° C. 30 sec Rinse 35 ° C. 30 sec Rinse 35 ° C. 30 sec Drying 70 to 80 ° C. 60 seconds each processing solution is there.

Color developer Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3.0 g N, N-hydrazinodiacetic acid 5 g Sodium chloride See Table 2 Potassium bromide 0.02 g Potassium carbonate 25 g Triethanolamine 10 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g Fluorescent whitening agent (WHITEX-4 manufactured by Sumitomo Chemical Co., Ltd.) 0.7 g Sodium sulfite 0.1 g Add water 1000 ml pH (25 ° C) 10.05 Bleaching fixer Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Water was added and adjusted to pH (25 ° C.) 6.00 with 1000 ml glacial acetic acid.

Rinse solution Ion-exchanged water (3 ppm or less for each of calcium and magnesium) The samples were processed by changing the amount of sodium chloride in the color developer as shown in Table 2.

For the treated sample, the amount of residual silver in the maximum density part (Dmax) was measured by X-ray fluorescence in order to evaluate the amount of residual silver.

Furthermore, the maximum density (D _G max) and the minimum density (D _G max) of magenta
_G min) was measured with a Macbeth densitometer. The results are shown in Table 2.

By processing the samples 1-D, 1-F, and 1-G of the present invention with a color developer having a chloride ion in the region of the present invention, the residual silver amount and the magenta fog are small and the maximum density is high. Photographic characteristics can be obtained.

(Example 2) Using samples 1-E and 1-G of Example 1, a processing solution was used in which the concentrations of sodium sulfite and sodium chloride in the color developer were changed as shown in Table 3. Processing was performed in the same manner as in Example 1 except for the amount of residual silver and the maximum density of cyan (D _R ma
Table 3 shows the measurement results of x).

According to the present invention, the desilvering property is improved and a sufficient color-forming density can be obtained. In particular, the sulfite ion concentration is 3 × 10 ⁻³ M
Notable below. The effect of the present invention cannot be obtained in the sample 1-E having a coefficient of variation of 0.20.

(Example-3) Silver halide emulsion of blue-sensitive silver halide emulsion layer (1)
Was prepared as follows.

(2 liquids) Sulfuric acid (1N) 20cc (3 liquids) The following compound (1%) 3cc (Liquid 1) was heated to 60 ° C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 60 minutes. 10 minutes after the addition of (liquid 4) and (liquid 5),
(Sixth solution) and (Sixth solution) were simultaneously added over 25 minutes. Five minutes after the addition, the temperature was lowered and desalted. Water and dispersed gelatin were added, the pH was adjusted to 6.0, and the average particle size variation coefficient was 1.0 μm (standard deviation divided by average particle size; s /) 0.1
1 μm coefficient of variation (standard deviation divided by average particle size;
Thus, a monodispersed cubic silver chlorobromide emulsion having an s /) of 0.11 and 1 mol% of silver bromide was obtained. Triethylthiourea was added to this emulsion to perform optimum chemical sensitization. Thereafter, the following spectral sensitizing dye (Sen-1) was added in an amount of 7 × 10 5 per mol of the silver halide emulsion.
^-4 mol was added.

Silver halide emulsion of green-sensitive silver halide emulsion layer (2)
The silver halide emulsion (3) of the red-sensitive silver halide emulsion layer was prepared in the same manner as described above, except that the amount of the chemical, the temperature and the addition time were changed.

For the silver halide emulsion (2), a spectral sensitizing dye (Sen
-2) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion, and for the silver halide emulsion (3), a spectral sensitizing dye (Sen-3) was added in an amount of 0.9 × 10 ^-4 mol per mol of the emulsion. .

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (3) are as shown below.

Then, a blue-sensitive silver halide emulsion (4) was prepared as follows.

(8 solutions) H ₂ O 1000 ml NaCl 49 g KBr 0.88 g K ₂ IrCl ₆ (0.001%) 2 ml Gelatin 25 g (9 solutions) Sulfuric acid (1N) 3 ml (10 solutions) AgNO ₃ 125 g Add water 450 ml (8 solutions) was heated to 60 ° C. and (9 solutions) was added. Thereafter (10 solutions) was added over 60 minutes, and 10 minutes after the addition, the temperature was lowered to desalinate, and an emulsion (4) was prepared in the same manner as the emulsion (1).

The silver halide emulsion (5) of the green-sensitive silver halide emulsion layer and the silver halide emulsion (6) of the red-sensitive silver halide emulsion layer were prepared in the same manner as described above.
It was prepared by changing the temperature and the addition time.

For the silver halide emulsion (5), a spectral sensitizing dye (Sen
-2) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion, and for the silver halide emulsion (6), a spectral sensitizing dye (Sen-3) was added in an amount of 0.9 × 10 ^-4 mol per mol of the emulsion. .

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (4) to (6) are as shown below.

Using the prepared silver halide emulsions (1) to (6),
A multilayer color photographic tourist material having the following layer structure was prepared. The coating solution was prepared as follows.

First layer coating liquid preparation solution Ethyl acetate (27.2 CC) and solvent (Solv-1) (3.8 CC) were added to 19.1 g of Yellow Coupler (ExY) and dissolved.
10% containing 0% sodium dodecylbenzenesulfonate 8CC
% Gelatin aqueous solution 185CC. On the other hand, a blue-sensitive sensitizing dye (Sen-1) was added to silver halide emulsion (1).
A solution prepared by adding 5.0 × 10 ⁻⁴ mol per mol was prepared. The emulsified dispersion and the emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardener for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following compounds were added to the red-sensitive emulsion layer in an amount of 1.9 × 10 ⁻³ mol per mol of silver halide.

Further, to the blue-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.0 × 10 ^-2 mol per mol of silver halide.

Also, the blue-sensitive emulsion layer and the green-sensitive emulsion layer are
(5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 1.0 × 10 5 per mol of silver halide.
^-3 mol and 1.5 × 10 ^-3 mol were added.

To the red-sensitive emulsion layer, 2.5.times.10.sup.- ⁴ mol of 2-amino-5-mercapto-1,3,4-thiadiazole was added per mol of silver halide.

 The composition of each layer is shown below.

(Layer composition) Support Paper support laminated on both sides with polyethylene [White pigment: TiO ₂ (2.7 g / m ² ) on polyethylene on first layer side]
And blue dye (ultra blue)] First layer (blue-sensitive layer) Silver halide emulsion (1) or (4) See Table 4 Gelatin 1.13 Yellow coupler (ExY) 0.66 Solvent (Solv-1) 0.28 Second Layer (color mixture prevention layer) Gelatin 0.89 Color mixture prevention agent (Cpd-1) 0.08 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.20 Dye (T-1) 0.005 Third layer (green sensitive layer) Silver halide emulsion (2) or (5) See Table 4. Gelatin 0.99 Magenta coupler (ExM-1) 0.25 Color image stabilizer (Cpd-2) 0.10 Color image stabilizer (Cpd-3) 0.05 Color image stabilizer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.01 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.15 Fourth layer (ultraviolet absorbing layer) Gelatin 1.42 Ultraviolet absorbing agent (UV-1) 0.52 Color mixing inhibitor (Cpd- 1) 0.06 Solvent (Solv-4) 0.26 Dye (T-2) 0.015 Fifth layer (Red-sensitive layer) Silver halide emulsion (3) or (6) Fourth Reference Gelatin 1.06 Cyan coupler (ExC-1) 0.16 Cyan coupler (ExC-2) 0.13 Color image stabilizer (Cpd-6) 0.32 Color image stabilizer (Cpd-7) 0.18 Solvent (Solv-4) 0.10 Solvent (Solv- 5) 0.10 Solvent (Solv-6) 0.11 Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorber (UV-1) 0.18 Solvent (Solv-4) 0.08 Dye (T-2) 0.005 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree
17%) 0.05 Liquid paraffin 0.03 The structure of the compound used is as follows.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Glacial acetic acid 9 g In addition 1000 ml pH (25 ℃) 5.40 Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.01 g Copper sulfate 0.005 g Ammonia water (28%) 2.0 ml Add water 1000 ml pH (25 ° C) 4.0 Samples shown in Table 4 using the above emulsion 3-A to 3-E were produced.

After imagewise exposing the above Samples 3-A to 3-E, continuous processing (running test) was carried out until replenishment of twice the tank capacity of the color developer in the following processing steps. Increase in minimum density of yellow (ΔD _B
min) and the amount of silver remaining (mg / cm ² ) in the maximum density part at the end of running are shown in Table 5. Further, the degree of generation of floating matter due to silver in the color developer at the end of running was visually shown.

In 3-D and 3-E using the emulsion of the present invention, the desilvering property is excellent, the increase in yellow density is extremely small, and the effect is remarkable. Also, there is no generation of floating silver.

Claims (1)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, comprising the steps of:
Containing more mole%, variation coefficient for grain size of the silver halide grains have at least one layer monodispersed silver halide emulsion is 0.15 or less, the amount of coated silver per 1 m ² is 0.80 g / m ² or less A silver halide color photographic light-sensitive material is prepared using a color developer having a chloride ion concentration of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / and a sulfite ion concentration of 0 to 3 × 10 ^-3 mol /. A method for processing a silver halide color photographic light-sensitive material, characterized by processing.