JP3078154B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a "light-sensitive material"). The present invention relates to a processing method using bleach-fixing in which crystal precipitation is prevented on the walls and edges of a bath.

[0002]

2. Description of the Related Art Processing of a silver halide color photographic light-sensitive material basically consists of two steps of color development and desilvering, and desilvering is a bleaching and fixing step, or a single-bath bleaching used in combination or alone. It consists of a fixing process. If necessary, additional processing steps such as water washing, stop processing, stabilizing processing, and pre-processing for promoting development are added. In recent years, reductions in the amount of replenishment of bleach-fixing solution and the amount of waste liquid have been strongly desired for the purpose of speeding up bleach-fixing processing, reducing environmental pollution, saving resources, and reducing costs. However, in reality, the situation is not low replenishment and low waste liquid. The main reason for this is that low replenishment increases the residence time of the processing solution in the bleach-fix bath, causing stains due to the reduction of sulfite, and in severe cases, precipitation of sulfur and silver sulfide. And the problem that the mixing ratio of the color developing solution is increased, the desilvering property is reduced, and the precipitation of crystals on the walls and edges of the bleach-fix bath is likely to occur.

For the purpose of improving the stability of the bleach-fix solution, patents relating to carbonyl bisulfite adducts have been filed (Japanese Patent Application Laid-Open Nos. 48-43733 and 50-5).
Nos. 1326 and 56-107244, JP-A-1-26
No. 7540, JP-A-3-233451). However, with the above technology, the improvement of the stability of the bleach-fix solution is insufficient,
Significant low replenishment of the photosensitive material 1 m ² per 20 to 150 ml is not always possible. In particular, p
The stability of the bleach replenisher with low H is insufficient, and when the concentration of a preservative such as a sulfite or carbonyl bisulfite adduct is increased, the desilvering property is reduced or crystal precipitation is likely to occur. Occurs. In recent years, there has been no technology capable of remarkably reducing the amount of replenishment even in the case of a small processing volume and a long residence time in minilabs that have been introduced to the market in recent years, and new technology development has been required.

[0004]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a processing method in which the stability of a bleach-fix solution is improved and the replenishment amount is significantly reduced. Also, the second
An object of the present invention is to provide a processing method having a good desilvering property. A third object is to reduce the precipitation of crystals in a developing machine tank.

[0005]

Means for Achieving the Object The present inventors have studied the above object and found that the object can be achieved by the following processing method. (1) A method in which an exposed silver halide color photographic material is processed with a color developing solution and then with a bleach-fixing solution, wherein the bleach-fixing solution comprises Fe of a compound represented by the following general formula (I). (III) containing complexes, method for processing a silver halide color photographic material, wherein the replenishing amount of the bleach-fixing bath is photosensitive material 1 m ² per 20-150 ml. General formula (I)

[0006]

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(2) The treatment method according to (I), wherein the [S, S] form is selectively used among the optical isomers of the compound of the formula (I). (3) The processing method according to (1), wherein the pH of the bleach-fix replenisher is 4.0 to 5.5. (4) 90 mol% of silver halide color photographic light-sensitive material
The above is characterized by having at least one emulsion layer containing photosensitive silver halide grains composed of silver chloride (1)
The processing method described.

Hereinafter, the present invention will be described in detail. First, the bleach-fixing solution of the present invention will be described in detail below. The compound represented by formula (I) will be described in detail below.

The aliphatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. One to ten is preferred. It is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group and an ethyl group. R ₁ , R
_The aromatic group represented by ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, for example, a phenyl group and a naphthyl group, and a phenyl group is more preferred. The aliphatic group and the aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may have a substituent, for example, an alkyl group (eg, methyl, ethyl) Aralkyl group (eg, phenylmethyl), alkenyl group (eg, allyl), alkynyl group, alkoxy group (eg, methoxy, ethoxy), aryl group (eg, phenyl, p-methylphenyl), amino group (eg, dimethylamino), acylamino group (Eg acetylamino),
A sulfonylamino group (eg, methanesulfonylamino), a ureido group, a urethane group, an aryloxy group (eg, phenyloxy), a sulfamoyl (eg, methylsulfamoyl), a carbamoyl group (eg, carbamoyl, methylcarbamoyl), an alkylthio group (methylthio), Arylthio group (eg, phenylthio), sulfonyl group (eg, methanesulfonyl), sulfinyl group (eg, methanesulfinyl), hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono Group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxycarbonyl group (eg, methoxycarbonyl), acyloxy group (eg, Butoxy), a carbonamido group, a sulfonamido group, a nitro group, such as hydroxamic acid group and, where possible may be the dissociated form or salt. When the substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ , R ₂ , R
₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom. The divalent linking group represented by W can be preferably represented by the following general formula (W). Formula (W)-(W ¹ -D) _m- (W ² ) _n-wherein W ¹ and W ² may be the same or different and have a straight or branched chain having 2 to 8 carbon atoms. Alkylene group (eg, ethylene, propylene), a cycloalkylene group having 5 to 10 carbon atoms (eg, 1,2-cyclohexyl), an arylene group having 6 to 10 carbon atoms (eg, o-phenylene), aralkylene having 7 to 10 carbon atoms Group (eg, o-xylenyl), a divalent nitrogen-containing heterocyclic group or a carbonyl group. D is -O -, - S -, - represents a or a divalent nitrogen-containing heterocyclic group - N (R _W). R _W is a hydrogen atom or -COO
_{M a, -PO 3 M b M} c, -OH or -SO ₃ M _d
Represents an alkyl group having 1 to 8 carbon atoms (for example, methyl) or an aryl group having 6 to 10 carbon atoms (for example, phenyl) which may be substituted. M _a , M _b , M _c and M _d each represent a hydrogen atom or a cation. Examples of the cation include alkali metals (for example, lithium, sodium, and potassium), ammonium (for example, ammonium and tetraethylammonium), and pyridinium. The linking group represented by W may have a substituent, and examples of the substituent include those described as the substituents of R ₁ to R ₆ . The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the heteroatom is nitrogen, and more preferably a divalent nitrogen-containing heterocyclic group linked to W ¹ and W ² at a carbon atom such as an imidazolyl group. preferable.
As W ¹ and W ² , an alkylene group having 2 to 4 carbon atoms is preferable. m represents 0 or an integer of 1 to 3;
Or in the case of 3, W ¹ -D may be the same or different. m is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. n represents an integer of 1 to 3, and when n is 2 or 3, W ² may be the same or different. n is preferably 1 or 2. Specific examples of W include, for example, the following.

[0010]

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[0011]

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The cations represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg, lithium, sodium, potassium), ammonium (eg, ammonium, tetraethylammonium), pyridinium and the like. .

In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited to these.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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The compound represented by the general formula (I) may be any optical isomer. [S, S] body, [S,
It may be an [R] -form, [R, S] -form or [R, R] -form, or a mixture of these isomers. For example,
The isomer of the exemplified compound (I-1) may be either [S, S] or [S, R], as described in the following literature.
R] form, or a mixture of these isomers. In order to reduce the amount of residual silver and stain, which is the object of the present invention, it is preferable to selectively use the [S, S] isomer among the optical isomers, as exemplified in compound (I-1). Particularly, a compound synthesized using an L-form amino acid as a raw material is preferable. [S, S] bodies are also preferable in that they are easily biodegradable. Here, “selective” means that 70% or more of the mixture of optical isomers is [S,
[S, S] form, more preferably 90% or more. The compound represented by the general formula (I) of the present invention can be synthesized according to the description in JP-A-63-199295 and JP-A-3-173857. These documents relate to a detergent composition using the compound represented by the general formula (I) of the present invention as a chelating agent, and its Fe (III) complex salt is used for bleaching for silver halide color photographic light-sensitive materials. There is no description that it is effective as an agent or the like. The method for selective synthesis of the [S, S] form is described by UMEZAWA et al. In THE JOURNAL OF ANTIBIOT.
ICS, Vol, XXXVII, No. 4, pp. 426 (APR. 1984) and the like can be easily synthesized. Next, specific examples of the Fe (III) complex salt used in the present invention are shown below, but the present invention is not limited to these.

[0021]

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[0022]

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The bleach-fixing composition used in the present invention may be a powder such as a kit or an aqueous solution such as a processing solution or a replenisher used in the processing.
The ferric complex used in the bleach-fixing solution may be added and dissolved as a complexed iron complex in advance, or a complex-forming compound and a ferric salt (for example, ferric sulfate, ferric chloride, etc.). Nitetsu,
Complex salts may be formed in the bleach-fixing solution by coexisting with ferric bromide, iron (III) nitrate, ammonium iron (III) sulfate and the like. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ions, and when it is added in excess, it is usually preferable to make the excess in the range of 0.01 to 10%.

The compound forming a ferric complex salt in the bleach-fixing solution (composition) of the present invention is preferably a compound represented by the above-mentioned general formula (I) in an amount of 50 mol% or more. Preferably, it accounts for 80 mol% or more.
In the present invention, as the compound forming the ferric complex salt in the bleach-fix solution, the compound represented by the above general formula (I) may be used alone or in combination of two or more. Good. Further, within the scope of the present invention, as the compound forming the ferric complex salt in the bleach-fix solution, a compound other than the compound represented by the above general formula (I) may be used in combination. Such compounds include EDTA, 1,3-
PDTA, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, Examples thereof include N- (2-carboxymethyl) iminodipropionic acid, but are not particularly limited thereto.

In the present invention, as the bleaching agent for the bleach-fixing solution, an inorganic oxidizing agent may be used in combination as the bleaching agent in addition to the above-mentioned ferric complex salt unless the object of the present invention is not impaired. Examples of such an inorganic oxidizing agent include hydrogen peroxide, persulfate, and bromate, but are not particularly limited thereto. The concentration of the ferric complex salt in the bleach-fix solution of the present invention is 0.005 to 0.5 mol /
The range of liter is appropriate, the range of 0.01 to 0.25 mol / liter is preferable, and the range of 0.0 to 0.25 mol / liter is more preferable.
It is in the range of 2 to 0.20 mol / liter. The concentration of the ferric complex salt in the replenisher is preferably 0.00
5 to 2 mol / l, more preferably 0.01 to 1.
0 mol / liter.

Next, a desilvering step applicable to the present invention will be described. In the present invention, the desilvering step includes a bleach-fixing step, and examples thereof include a bleach-fixing step, a bleach-bleach-fixing step, a bleach-fixing step-fixing step, a bleaching step-a bleach-fixing step-fixing step. In the present invention, it is preferable that the bleach-fixing step is used alone in terms of simplification and quickening of the desilvering step.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof, various compounds can be used as a bleaching accelerator. For example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide bond described in JP-B-45-8506 and JP-A-52-20832.
And thiourea compounds described in U.S. Pat. No. 3,706,561 or halides such as iodine and bromide ions are preferred in terms of excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or an iodide (eg, ammonium iodide). If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
One or more kinds of inorganic acids and organic acids having a pH buffering capacity such as citric acid, sodium citrate and tartaric acid, and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. Further, the bleach-fixing solution may contain other various kinds of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. 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 liter is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
1.01.0 mol.

The bleach-fixing solution or the fixing solution may be a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite), a bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite), a preservative. It preferably contains a sulfite ion releasing compound such as a bisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are converted to sulfite ions from about 0.02 to
The content is preferably 0.05 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative in a bleach-fixing solution or a fixing solution,
Sulfite is generally added, but ascorbic acid, carbonyl bisulfite adduct or carbonyl compound may be added, and benzenesulfinic acid is also effective. Furthermore, a buffering agent is used for the bleach-fixing solution and the fixing solution.
An optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

In the present invention, it is particularly preferred that the bleach-fixing solution contains substantially no ammonium ion from the viewpoint of preventing precipitation and improving the adhesion of the photographic material after processing. To be substantially free of ammonium ions,
0.1 mol / liter or less, 0.05
It is more preferably at most mol / l, most preferably not containing at all. In the bleach-fix solution of the present invention, the preferable pH range is 3 to 10, and more preferably 4 to 10.
To 9 are preferred. Among them, when a high silver chloride emulsion is used for the light-sensitive material, the pH of the bleach-fixing solution is preferably from 7.0 to 4.0, and particularly preferably from 6.5 to 4.0. In addition, the pH of the bleach-fixing solution is reduced by reducing the amount of replenishment to the bleach-fixing bath.
In order to maintain the pH below 5, it is necessary to further lower the pH of the bleach-fix replenisher.
Particularly preferred is 5.5. Until now, there was a problem that stability was poor when the pH of the bleach-fixing replenisher was 4.0 to 5.5. However, by using the compound of the general formula (I) of the present invention as an iron complex salt, the stability was poor. Use of a bleach-fix replenisher having a pH of 4.0 to 5.5,
For the first time, low replenishment processing with excellent desilvering and stability has become possible. The replenishment rate to the bleach-fix bath of the present invention is 1 m ² of the light-sensitive material.
20 to 150 milliliters per bottle. Particularly preferably, it is 25 to 100 ml, and further preferably, 30 to 50 ml. The processing temperature of the bleach-fix solution applicable to the present invention is from 20 to 50C, preferably from 30 to 40C. The processing time is 10 seconds to 5 minutes, preferably 20 seconds to 2 minutes.

Next, the color developer used in the present invention will be described. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, and typical examples are N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-N-lauryl). Amino) toluene, 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N
-Ethyl-N- (β-hydroxyethyl) amino] aniline, 4-amino-3-methyl-N-ethyl-N- [β
-(Methanesulfonamido) ethyl] -aniline, N-
(2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline, 4-amino-3-methyl-
Examples thereof include N-ethyl-N-β-ethoxyethylaniline and 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline. Particularly preferably 4
-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -aniline. Also,
These p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent to be used is generally about 4 to 50 mmol per liter of the color developing solution. Is about 21 mmol to 45 mmol, more preferably about 23 mmol to 40
It is a concentration of millimolar. The method of the present invention is particularly effective in the case of a concentrated color developing replenisher.

In practicing the present invention, work environment
It is preferable to use a color developer which does not substantially contain benzyl alcohol. Here, "substantially not contained" means preferably 2 ml / liter or less, more preferably
A benzyl alcohol concentration of 0.5 ml / liter or less, most preferably no benzyl alcohol at all.

The color developer used in the present invention must be substantially free of sulfite ions in order to suppress fluctuations in photographic characteristics due to continuous processing. × 10 ^-3 mol / liter or less). Most preferably, it contains no sulfite ions. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The color developer used in the present invention preferably does not substantially contain sulfite ions. However, in order to suppress a change in photographic characteristics due to a change in the concentration of hydroxylamine, the color developer further contains substantially hydroxylamine. (Substantially not contained herein means that the hydroxylamine concentration is 5.0 × 10 ⁻³ mol / liter or less.)
Is more preferred. Most preferably it contains no hydroxylamine.

The color developer used in the present invention more preferably contains an organic preservative in place of the hydroxylamine and sulfite ions. Here, the organic preservative refers to any organic compound that reduces 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), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones,
Organic preservatives particularly effective for α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused ring amines, etc. It is. These are JP-B-48-30496 and JP-A-52-143020.
Nos. 63-4235, 63-30845, 63-21647, 63
-44655, 63-53551, 63-43140, 63-56654
No. 63-58346, No. 63-43138, No. 63-146041, No.
Nos. 63-44657, 63-44656, U.S. Pat.No. 3,615,503,
No. 2,494,903, JP-A-1-97953, 1-186939,
Nos. 1-186940, 1-187557, and 2-306244. Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, JP-A-63-239447 and JP-A-63-39447. −
No. 128340, amines as described in JP-A-1-186939 and JP-A-1-187557, alkanolamines as described in JP-A-54-3532, polyethyleneimines as described in JP-A-56-94349, An aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544 or the like may be used if necessary. In particular, alkanolamines such as triethanolamine, N, N-
Diethylhydroxylamine or N, N-di (sulfoethyl)
Addition of dialkylhydroxylamine such as hydroxylamine, hydrazine derivative (excluding hydrazine) such as N, N-bis (carboxymethyl) hydrazine, or aromatic polyhydroxy compound such as sodium catechol-3,5-disulfonate Is preferred.

In particular, it is more preferable to use a dialkylhydroxylamine and / or a hydrazine derivative in combination with an alkanolamine in terms of improving the stability of the color developing solution and further improving the stability during continuous processing. .

In the present invention, chlorine ion is contained in the color developer.
3.0 × 10^-2~ 1.5 × 10^-1Mol / l
Is preferred. Particularly preferably, 3.5 × 10^-2~ 1 × 10^-1
Mol / l. Chloride ion concentration is 1.5 × 10^-1~
Ten^-1If it is more than mol / liter, it will delay development.
It has disadvantages and is not preferred. Also, 3.0 × 10^-2Mol / liter
If the pressure is less than torr, it is not preferable in preventing fog. Book
In the present invention, 3.0 × 10
^-FiveMol / l to 1.0 × 10^-3Contains mol / l
Is preferred. More preferably, 5.0 × 10 ^-Five~ 5 × 10
^-FourMol / l. Bromine ion concentration 1 × 10^-3Mo
If the amount is greater than liters / liter,
And sensitivity drop, 3.0 × 10^-FiveLess than mol / l
In such a case, fog cannot be sufficiently prevented.

Here, chlorine ions and bromine ions may be added directly to the color developer, or may be eluted from the photosensitive material into the color developer during the development processing. When directly added to a color developer, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. As a bromine ion supply substance,
Examples include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the photosensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion,
They may be supplied from sources other than emulsions.

The color developer used in the present invention preferably has a pH of 9 to 12, and more preferably 9 to 11.0. The color developer may contain other known compounds of developer components. it can. In order to maintain the above pH,
It is preferable to use various buffers. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt,
Leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane Salts, lysine salts and the like can be used. In particular, carbonate, phosphate, tetraborate, hydroxybenzoate is excellent in solubility, buffer capacity in a high pH region of pH 9.0 or more,
Even when added to a color developer, it has the advantage that it has no adverse effect on photographic performance (such as fog) and is inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The amount of the buffer added to the color developer is preferably at least 0.1 mol / l, and particularly preferably from 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include diacetic acid and hydroxyethyliminodiacetic 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 the metal ions in the color developer.
For example, it is about 0.1 g to 10 g per liter.

An optional development accelerator can be added to the color developer if necessary. As a development accelerator,
No. 6088, No. 37-5987, No. 38-7826, No. 44-12380,
Thioether compounds represented by JP-A-45-9919 and U.S. Pat.No. 3,813,247, JP-A-52-49829 and JP-A-50-1498
P-phenylenediamine-based compound represented by No. 5554,
JP-A-50-137726, JP-B-44-30074, JP-A-56-15
Quaternary ammonium salts represented by Nos. 6826 and 52-43429; U.S. Pat.Nos. 2,494,903; 3,128,182;
4,230,796, 3,253,919, JP-B-41-11431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,34
Amine compounds described in No. 6, etc., JP-B-37-16088,
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
And polyalkylene oxides described in U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. Benzyl alcohol is as described above.

In the present invention, an optional antifoggant can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer applicable to the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g.
/ Liter. If necessary, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, and polyalkyleneimine may be added.

The processing temperature of the color developing solution applicable to the present invention is 20 to 50 ° C., preferably 30 to 40 ° C. Processing time is
It is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 30 to 200 ml, more preferably 1 to ² m2 of the light-sensitive material.
30 ml to 150 ml. Next, the washing and / or stabilizing step used in the present invention will be described.

In the present invention, after desilvering such as fixing or bleach-fixing, washing and / or stabilization are performed. The replenishment amount in the washing step or the stabilization step is 3 to 50 times, preferably 3 to 30 times, the carry-in amount from the previous bath per unit area of the photosensitive material. More preferably, it is 3 to 10 times. In the case of performing the stabilization treatment after washing with water, the method of the present invention is effective in a treatment system in which at least the stabilization step in the final step is 3 to 50 times. Replenishment may be performed continuously or intermittently. The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid. The amount of rinsing water in the rinsing step may vary depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to a range. Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 liter to 1 liter per 1 m ^{2 of the} photosensitive material.
Although liters or less are possible, there is a problem in that, due to an increase in the residence time of water in the tank, bacteria proliferate and generated floating substances adhere to the photosensitive material. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-1201
Chlorinated bactericides such as chlorinated sodium isocyanurate described in No. 45, benzotriazole described in JP-A-61-26761, copper ions and others.
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2). Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution immediately after the above-mentioned washing step or directly without passing through the washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH to a level suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. , All can be used.
In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

The preferred pH of the washing step or the stabilizing step is 4
-10, and more preferably 5-8. The temperature can be variously set depending on the application and characteristics of the photosensitive material, but generally ranges from 15 to
45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. It is preferably 15 seconds to 1 minute and 45 seconds, and more preferably 30 seconds to 1 minute and 30 seconds.

The treating agent applicable to the present invention may be supplied as a concentrated liquid having a single or plural part composition, or may be supplied as a powder. Further, it may be supplied in the state of a used liquid, or may be a combination of a concentrated liquid, a powder, and a used liquid.

As the material of the replenishment cartridge for filling the processing liquid used in the present invention, any material such as paper, plastic, metal and the like can be used. In particular, the oxygen permeation coefficient is 50 ml / (m ² · atm · day). The following plastic materials are preferred: The oxygen permeability coefficient is “O ₂ permeation of plastic container, modern packing” (O ₂ permeation of plastic container).
iner, Modern Packing; NJCalyan, 1968)
It can be measured by the method described in Monthly Pages 143 to 145. Preferable examples of the plastic material include vinylidene chloride (PVDC) and nylon (N
Y), polyethylene (PE), polypropylene (P
P), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVAL), polyacrylonitrile (PAN),
Examples thereof include polyvinyl alcohol (PVA) and polyethylene terephthalate (PET). In the present invention, in order to reduce oxygen permeability, PVDC, NY, P
The use of E, EVA, EVAL and PET is preferred. These materials may be used singly and formed and used, or a method of forming a film and bonding a plurality of kinds (a so-called composite film) may be used. Further, as the shape of the container, various shapes such as a bottle type, a cubic type, and a pillow type can be used, but the present invention provides a cubic type which is flexible, easy to handle, and can be reduced in volume after use. Structures similar to are particularly preferred. When used as a composite film, the following structures are particularly preferred, but are not limited thereto.・ PE / EVAL / PE ・ PE / aluminum foil / PE ・ NY / PE / NY ・ NY / PE / EVAL ・ PE / NY // PE / EVAL / PE ・ PE / NY / PE / PE / PE / NY / PE・ PE / SiO ₂ film / PE ・ PE / PVDC / PE ・ PE / NY / aluminum foil / PE ・ PE / PP / aluminum foil / PE ・ NY / PE / PVDC / NY ・ NY / EVAL / PE / EVAL / NY・ NY / PE / EVAL / NY ・ NY / PE / PVDC / NY / EVAL / PE ・ PP / EVAL / PE ・ PP / EVAL / PP ・ NY / EVAL / PE ・ NY / aluminum foil / PE ・ Paper / aluminum foil / PE ・ Paper / PE / Aluminum foil / PE ・ PE / PVDC / NY / PE ・ NY / PE / Aluminum foil / PE ・ PET / EVAL The thickness of the PE · PET / aluminum foil / PE · PET / aluminum foil / PET / PE the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns.
Further, the content of the completed container is about 100 to 20 liters, preferably about 500 to 10 liters. The container (cartridge) may have a cardboard or plastic outer box, or may be formed integrally with the outer box. The cartridge of the present invention can be filled with various processing liquids. For example, a color developer, a black-and-white developer, a bleaching solution, an adjusting solution, a reversal solution, a fixing solution,
A bleach-fixing solution, a stabilizing solution and the like can be mentioned, but it is preferable to use a color developing solution, a black-and-white developing solution, a fixing solution and a bleach-fixing solution particularly for a cartridge having a low oxygen permeability coefficient.

Next, the photosensitive material that can be used in the present invention will be described. The present invention can be applied to any photosensitive material. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangements, etc.) applied in the present invention, and the processing methods and processing additives applied for processing this light-sensitive material include: And the following patent publications, in particular, European Patent EP 0,355,660 A2 (Japanese Patent Application No. 1-107).
No. 011) is preferably used.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

[Table 5]

The silver halide emulsion used in the present invention is
It is preferable to have at least one emulsion layer containing silver halide grains in which 90 mol% or more is made of silver chloride.
An emulsion comprising preferably 95 to 99.9 mol% or more, more preferably 98 to 99.9 mol% or more of silver chloride, and a chlorobromide in which the whole layer comprises 98 to 99.9 mol% or more of silver chloride. Particularly preferred is a silver emulsion. The amount of silver applied is not particularly limited, but is preferably about 0.4 to 0.7 g / m ² . Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in No. 33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0,333,185 A2 (among others, a 4-equivalent coupler of the coupler (42) listed as a specific example) is chlorinated. 2 equivalents with a leaving group, couplers (6)
And (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 are particularly preferred). .

The light-sensitive material according to the present invention can be decolorized on a hydrophilic colloid layer by a process described in EP 0,337,490A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (especially oxonol dyes) are added so that the optical reflection density at 680 nm of the photosensitive material is 0.70 or more, and dihydric alcohols (2 to 4) are added to the water-resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with, for example, trimethylolethane). Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inert and substantially colorless compound, and / or
Alternatively, a compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine-based color developing agent remaining after color development processing is used simultaneously or independently. However, it is preferable in order to prevent, for example, the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler during storage after processing. Further, to the photosensitive material according to the present invention, a fungicide such as described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Is preferred.

In the present invention, the swelling degree of the photographic layer of the silver halide color light-sensitive material is preferably 1.2 to 3.0.
It is particularly preferable from the viewpoint of improving the adhesion of the processed color light-sensitive material. The lubricity of the present invention is a value obtained by dividing the thickness of the photographic layer after immersing the color photographic material in distilled water at 33 ° C. for 2 minutes by the thickness of the dried photographic layer. More preferably, it is 1.3 to 2.7.

The photographic layer herein means a laminated hydrophilic colloid group containing at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. It does not include the back layer provided on the side opposite to the photographic photosensitive layer across the support. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and includes an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like in addition to the silver halide emulsion layer.

To adjust the swelling degree to any of the above, any method may be used. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer Or by changing the aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. As the gelatin derivative, for example, acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides and epoxy compounds are used.

As the gelatin / graft polymer, a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. What was made can be used. In particular, a graft polymer of a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacryl methacrylate is preferable.
Examples of these are disclosed in U.S. Pat.
31, 767 and 2,956,884. Representative synthetic hydrophilic polymeric substances are described, for example, in West German Patent Application (OLS) 2,312,708, U.S. Pat.
No. 620, 751, No. 3, 879, 205;
No. 3-7561.

Examples of the hardener include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane Derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide], active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid and mucofenoxycyclolic acid), isoxazoles, and dialdehyde starch; 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardening agents include aldehydes,
Active vinyl compounds and active halogen compounds.

The color light-sensitive material used in the present invention includes color paper, color reversal paper, direct positive color light-sensitive material, color negative film, color reversal film and the like. Preferably, it is a color photographic material for printing such as color paper. Further, as the support used in the light-sensitive material according to the present invention, a white polyester-based support for a display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used. May be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. Especially so that the display can be viewed with both reflected and transmitted light,
The transmission density of the support is preferably set in the range of 0.35 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred. In the exposure, it is preferable to use a band stop filter described in U.S. Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

[0070]

Next, the present invention will be described in detail with reference to examples. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer structure shown below. Was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-
7) 27.2 cc of ethyl acetate and solvent (So
iv-3) and 4.1 g of (Solv-7) were added and dissolved, and the resulting solution was dissolved in a 10% aqueous solution of gelatin 185 containing 8 cc of 10% sodium dodecylbenzenesulfonate.
The resulting mixture was emulsified and dispersed in cc to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 emulsion of a large emulsion having an average grain size of 0.88 μm and a small emulsion of 0.70 μm)
Mixture (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and the silver bromide of each emulsion was 0.1.
3 mol% was localized on part of the particle surface).
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were used in an amount of 2.0.times.
10 ^-4 mol and 2.5 × 10 ^-4 mol were added to small-size emulsion A, respectively. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer.
The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition.

The 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.

Each layer has Cpd-10 and Cpd-11.
Was added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer.

[0075]

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(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion A and 2.5 × 10 ^-4 mol for small-size emulsion A, respectively)

[0077]

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(4.0 × 10 ^-4 mol for large-size emulsion B and 5.6 × 10 ^-4 mol for small-size emulsion B per mol of silver halide) and

[0079]

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(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion B, 1.0 × 10 ⁻⁵ mol for small-size emulsion B)

[0081]

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(Per mol of silver halide: 0.9 × 10 ^-4 mol for large-size emulsion C, and 1.1 × 10 ^-4 mol for small-size emulsion C)

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.

[0084]

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol per mol,
2.5 × 10 ^-4 mol was added.

The blue-sensitive emulsion layer and the green-sensitive emulsion layer were treated with 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0088]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv) -3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixture prevention layer) Gelatin 0.64 Color mixture inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (Ag molar ratio)) The variation coefficients of the grain size distribution were 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each emulsion. 0.12 Gelatin 1.28 Magenta coupler (ExM) ) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0 .02 Solvent (Solv-2) 0.40

Fourth layer (ultraviolet absorbing layer) Gelatin 1.41 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-size emulsion having an average grain size of 0.58 μm and small-size emulsion of 0.45 μm (Ag molar ratio)) The coefficient of variation of the grain size distribution was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on part of the grain surface.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.10 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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After imagewise exposure of the above photosensitive material, continuous processing (running test) was performed in the following processing steps using a paper processing machine. The processing amount was 100 m ² of photosensitive material per week, and a running test was performed for 4 weeks. The bleach-fixing solution was tested by changing the replenishing amount. Replenishing solutions A to E were used so that the iron complex salt concentration, thiosulfate concentration and pH under running equilibrium were the same. (Refer to Table 6) Processing process Temperature Time Replenishment amount ^* Tank capacity Color development 38.5 ° C 45 seconds 73 ml 5 liter Bleaching and fixing 35.0 ° C 45 seconds See Table 6 5 liter Rinse (1) 35.0 ° C 20 seconds-3 liter from 3 liters rinse (4) 35.0 replenishing amount of ° C. 30 seconds 242 ml 3 l * photosensitive material 1 m ² per (rinse (4) - rinse (2) 35.0 ° C. 20 seconds - 3 liters rinse (3) 35.0 ° C. 20 seconds (The four-tank countercurrent method was adopted for (1).)

[0105]

[Table 6]

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Fluorescent whitening agent (WHITEX 4 manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfo Natoethyl) hydroxylamine 5.0 g 10.0 g Triisopropylnaphthalene (β) sodium sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 Sulfuric acid / monohydrate 5.0g 11.5g Add water 1000ml 1000ml pH (25 ℃ / potassium hydroxide and sulfuric acid T) 10.00 11.00

[Rinse solution] (The tank solution and the replenisher are the same.) 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity: 5 μs / cm or less) 1000 ml pH 6.5 A sensitometer (Fuji Photo Film Co., Ltd.) Made by company,
A step wedge exposure was given using a FWH type, light source color temperature of 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

After the completion of the running test, the samples were processed by the same automatic processor, and desilvering properties and stain were evaluated by the following methods. Desilverability: The amount of silver remaining at the maximum concentration point of the sample was measured by X-ray fluorescence analysis. Stain: The yellow density was measured by using a Macbeth densitometer in an unexposed portion of the sample. Next, the sulfite ion concentration in the bleach-fix solution after the running test was analyzed by an iodometry method, and the stability of the solution was evaluated. Table 7 summarizes the above results.

[0109]

[Table 7]

As shown in Table 7, when the replenishment amount of the bleach-fixing solution was remarkably reduced to 150 to 30 ml / m ^{2 of the} light-sensitive material, ethylenediaminetetraacetic acid, which has been conventionally used in general, had a preservative. The concentration of a certain sulfite ion is very low, and the processed photosensitive material shows an increase in yellow stain, and also has a degraded desilvering property. (Experiment N
o.1-5). However, when the compound of the present invention is used,
Even when the replenishing amount is 150 to 30 ml / m ² , good liquid stability and desilvering properties are exhibited, and the effect of the present invention is shown. (Experiment No. 6, 4
(See 7, 8, 9, 10, 11, 12, 13 or 14)
Nos. 9, 1 using only the [S, S] form of (I-1)
Nos. 0 and 11 show particularly excellent performance in desilvering, suppressing the increase in stain, and deteriorating sulfite.

Example 2 The bleach-fix tank solution after the completion of the running tests of Experiment Nos. 3 to 11 of Example 1 was used to measure the inner size of 5 cm × 10 cm × 50 cm.
(Depth) Put 2 liters each in a polyvinyl chloride container, place a float made of polyvinyl chloride so that the area where the liquid comes into contact with air is 10 cm ^2, and place it in a 40 ° C constant temperature bath. Left for a week. One week and two weeks after standing
The sulfite ion concentration of each liquid was measured in the same manner as in Example 1, and a precipitate or turbidity in the liquid was observed. Table 8 shows the results.

[0112]

[Table 8]

As shown in Table 8, when the bleach-fixing solution of Example 1 having a processing amount of 100 m ² per week was aged, the ethylenediaminetetraacetic acid which has been conventionally used in general was 1 hour after the aging. Sulfite ions, which are preservatives, almost disappeared in a week, and the solution became turbid, and a precipitate occurred two weeks after the lapse of time. This shows a situation when the processing amount is further reduced, and it is impossible to perform a small amount processing with a replenishment amount of the bleach-fixing solution of 150 to 30 ml / m ^{2 from} the viewpoint of stability. It is shown. However, when the compound of the present invention is used, even two weeks after aging,
The concentration of the sulfite ion, which is a preservative, is sufficiently high, the liquid is not turbid, the state is in good condition, and it is possible to reduce the processing amount with a replenishment amount of the bleach-fixing solution of 150 to 30 ml / m ^2. It is shown.

Example 3 A aging test was carried out in the same manner as in Example 2 using the bleach-fix replenisher shown below. [Bleach-fix replenisher] Water 400 ml Ammonium thiosulfate 176 ml Ammonium sulfite 70 g Chelating agent (see Table 9) 0.281 mol Ferric nitrate nonahydrate 0.264 mol Nitric acid (67%) 53 g Water was added. 1000ml pH (adjusted at 25 ℃ / nitric acid or ammonia) See Table 9

Each of the replenishers was 5 cm × 10 cm × 50 in depth.
Each 2 liters were placed in a 2 cm-cm polyvinyl chloride container, and a float made of polyvinyl chloride was placed so that the area where the liquid comes into contact with the air was 20 cm ^2, and left in a 40 ° C. constant temperature bath for 4 weeks. Two and four weeks after the standing, the sulfite ion concentration of each solution was measured in the same manner as in Example 2, and a precipitate or turbidity in the solution was observed. Table 9 shows the results.

[0116]

[Table 9]

As shown in Table 9, in the case of ethylenediaminetetraacetic acid, which has been generally used, the stability of sulfite ions is extremely poor at pH 5.5 or less, and precipitate or turbidity occurs after two weeks of aging. . However, when the compound of the present invention is used, pH in the range of 5.5 to 4.0
It shows almost the same stability as 6.0, and shows that the pH of the replenisher required for the lower replenishment of the bleach-fixer can be lowered. In the present invention, the pH of the replenisher is 4.0 to 4.0.
It turns out that 5.5 is more preferable.

Example 4 A multilayer color printing paper having the following layer constitution was produced on a paper support having a double-sided lamination with polyethylene and a corona discharge treatment on the surface. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer To 60.0 g of yellow coupler (ExY) and 28.0 g of anti-fading agent (Cpd-1), 150 cc of ethyl acetate, 1.0 cc of solvent (Solv-3) and 1.0 cc of solvent (Solv-
4) Add and dissolve 3.0 cc of this solution, and add this solution to a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate.
After adding to 50 cc, the mixture was dispersed with an ultrasonic homogenizer, and the obtained dispersion was mixed and dissolved in 420 g of a silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye. To prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-bis (vinylsulfonyl) ethane was used as a gelatin hardener for each layer.

The following were used as spectral sensitizing dyes for each layer. Blue-sensitive emulsion layer: anhydro-5,5'-dichloro-3,
3'-disulfoethylthocyanine hydroxide Green-sensitive emulsion layer: anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer: 3,3 ' -Diethyl-5-methoxy-
9,11-neopentylthiadicarbocyanine iodide

The following stabilizers were used as stabilizers for each emulsion layer. 1- (2-acetoamino-phenyl) -5-mercaptotetrazole 1-phenyl-5-mercaptotetrazole 7: 2: 1 mixture of 1- (p-methoxyphenyl) -5-mercaptotetrazole (molar ratio)

The following dyes were used as irradiation prevention dyes. [3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N '-(4,8-Dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonato) -tetrasodium salt [3-cyano-5-hydroxy -4- (3- (3-cyano-5-oxo-1- (4-sulfonatophenyl)-
2-pyrazolin-4-ylidene) -1-pentanyl)-
1-Pyrazolyl] benzene-4-sulfonate-sodium salt

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support A paper support laminated on both sides with polyethylene and subjected to corona discharge treatment on the surface

First layer (blue-sensitive layer) Silver chlorobromide emulsion described above (AgBr 0.7 mol%, cubic, average particle size 0.9 μm) 0.29 gelatin 1.80 yellow coupler (ExY) 0.60 anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03

Second layer (color mixture prevention layer) Gelatin 0.80 Color mixture prevention agent (Cpd-2) 0.055 Solvent (Solv-1) 0.03 Solvent (Solv-2) 0.15

Third Layer (Green Sensitive Layer) The above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average particle size 0.45 μm) 0.18 Gelatin 1.86 Magenta coupler (ExM) 0.27 Anti-fading agent (Cpd-3) 0.17 Anti-fading agent (Cpd-4) 0.10 Solvent (Solv-1) 0.2 Solvent (Solv-2) 0.03

Fourth layer (color mixture prevention layer) Gelatin 1.70 Color mixture prevention agent (Cpd-2) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent ( Solv-1) 0.05 Solvent (Solv-2) 0.05

Fifth Layer (Red Sensitive Layer) The aforementioned silver chlorobromide emulsion (AgBr 4 mol%, cubic, average particle size 0.5 μm) 0.21 gelatin 1.80 cyan coupler (ExC-1) 0.26 cyan Coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Color development accelerator (Cpd-5) 0.15

Sixth layer (ultraviolet absorbing layer) Gelatin 0.70 Ultraviolet absorbing agent (UV-1) 0.26 Ultraviolet absorbing agent (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv- 2) 0.09

Seventh layer (protective layer) Gelatin 1.07

(ExY) Yellow coupler α-pivalyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5- [β- (dodecylsulfonyl)
Butylamide] acetanilide (ExM) magenta coupler 7-chloro-6-isopropyl-3- {3-[(2-butoxy-5-tert-octyl) benzenesulfonyl] propyl} -1H-pyrazolo [5,1-c]- 1,2,4
-Triazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5 [2
-(2,4-di-tert-amylphenoxy) -3-methylbutylamidophenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-
Di-tert-amylphenoxy) butyramide] phenol

(Cpd-1) Anti-fading agent

[0135]

Embedded image

(Cpd-2) Color-mixing inhibitor 2,5-di-tert-octylhydroquinone (Cpd-3) Anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2 2,2'-spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color-developing agent p- (p-toluenesulfonamido) phenyl-dodecane

(Solv-1) solvent di (2-ethylhexyl) phthalate (Solv-2) solvent dibutyl phthalate (Solv-3) solvent di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide -Methoxy-2,4-
Di-t-amylbenzene

(UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5- Di-tert-butylphenyl) benzotriazole

These samples were exposed by the method described in Example 1, and the samples obtained by imagewise exposing the above photographic material separately were subjected to the following processing steps using a paper processing machine, and the tank capacity of the bleach-fix solution was obtained. A continuous process (running test) was performed until the replenishment was doubled, and then a process was performed to obtain a color image.

Processing process Temperature Time Replenishment amount ^* Tank capacity Color development 40 ° C 45 seconds 35 ml 7 liter Bleaching and fixing 30-36 ° C 45 seconds 30 ml 7 liter Stable 1 30-37 ° C 20 seconds −4 liter Stable 2 30 to 37 ° C. 20 seconds - 4 liters stable 3 30 to 37 ° C. 20 seconds - 4 liters stable 4 30 to 37 ° C. 30 seconds 120 ml 4 liters drying 70 to 85 ° C. 60 seconds * replenishment rate per photosensitive material 1 m ² (stable (4 → 1 4-tank countercurrent method)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 2.0 g 4.0 g 5,6-dihydroxybenzene-1,2,4-trisulfonic acid 0.3 g 0.5 g triethanolamine 8.0 g 8.0 g sodium chloride 10.0 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 25.0 g diethylhydroxylamine 4.2 g 10.0 g fluorescence Brightener (4,4'-diaminostilbene) 2.0 g 6.0 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 12.50

[Bleach-fixing solution] Tank solution Replenisher water 700 ml 400 ml ammonium thiosulfate (70%) 100 ml 200 ml ammonium sulfite 30 g 50 g [S, S] form of compound (I-1) 0.14 mol 0.28 mol Diiron 9-hydrate 0.13 mol 0.26 mol Nitric acid (67%) 30 g 50 g Add water 1000 ml 1000 ml pH (25 ° C) 6.0 4.6

[Stabilizing solution] (Tank solution and replenisher are the same) Formalin (37%) 0.1 g Formalin-sulfurous acid 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 1000 ml with water pH (25 ° C) 4.0 Good desilvering property, good white background from start to end of running test, Good results were obtained without liquid or crystal precipitation on the processor.

Example 5 In Example 4, even when an equimolar amount of (I-5), (I-9) or (I-12) was used in place of compound (I-1), good desilvering was achieved at the same time. The sex is obtained.

[0145]

According to the present invention, the stability of the bleach-fix solution has been improved, and processing with a replenishment amount significantly reduced has become possible. In particular, when the pH of the replenisher was lowered to 4.0 to 5.5, the stability was improved and good treatment was possible. Also, good desilvering properties could be obtained. The compounds used in the present invention have optical isomers, among which [S. When the [S] form is used as a main component, it is possible to obtain excellent effects such as improvement of desilvering property, suppression of stain, and stabilization of sulfite ions.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-224380 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 7/42

Claims (3)

(57) [Claims] 1. A method for processing an image-exposed silver halide color photographic light-sensitive material with a color developing solution and then with a bleach-fixing solution, wherein the bleach-fixing solution is represented by the following general formula (I). compounds [S, S] containing the Fe (III) complex salts of the body, the silver halide color photographic material, wherein the replenishing amount of the bleach-fixing bath is 20 to 150 ml photosensitive material 1 m ² per Processing method. General formula (I) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group.
W represents a divalent linking group containing a carbon atom. M ₁ , M ₂ , M
₃ and M ₄ each represent a hydrogen atom or a cation. ) 2. The pH of the bleach-fix replenisher is 4.0 to 5.5.
2. The processing method according to claim 1, wherein 3. A silver halide color photographic light-sensitive material comprising 9
2. The processing method according to claim 1, wherein the emulsion has at least one emulsion layer containing photosensitive silver halide grains in which 0 mol% or more is made of silver chloride.