JPH06123950A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability of a bleaching-fixing liq., to reduce a replenishment volume, to obtain excellent desilvering property and to reduce the precipitation of a crystal in a development processing device by incorporating a specified Fe (III) complex salt in the bleaching-fixing liq. and keeping the replenishment volume to a bleaching-fixing bath within a prescribed range. CONSTITUTION:In the method processing the exposed silver halide color photograph sensitive material with the bleaching-fixing liq. after processing with a color developer, a Fe (III) complex salt of the compd. expressed by the formula is incorporated in the bleaching-fixing liq., and the replenishment volume to the bleaching-fixing bath is kept in a 20-150ml range per 1m<2> photosensitive material. In the formula, R1-R6 is hydrogen atom, aliphat., arom. or hydroxy group respectively, W is a bivalent connecting group containing carbon atom, M1-M4 is each hydrogen atom or a cation respectively. And in the optical isomer of the compd. expressed by the formula, (S, S) type is used selectively.

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, also simply referred to as a light-sensitive material), which is particularly excellent in stability and desilvering property. The present invention relates to a processing method using bleach-fixing which prevents the precipitation of crystals on the walls and edges of the bath.

[0002]

BACKGROUND OF THE INVENTION The processing of silver halide color photographic light-sensitive materials basically comprises two steps of color development and desilvering. Desilvering is a bleaching and fixing step, or one-bath bleaching used in combination with these or alone. It consists of a fixing process. In addition to this, additional processing steps such as water washing, termination processing, stabilization processing, pretreatment for promoting development, and the like are added, if necessary. In recent years, reduction of the replenishing amount of the bleach-fixing solution and reduction of the amount of waste liquid have been strongly desired for the purpose of speeding up the bleach-fixing process, reduction of environmental pollution, resource saving and cost reduction. However, the reality is that low replenishment and low liquid waste have not been achieved. The main reason for this is that the retention time of the processing solution in the bleach-fixing bath becomes longer due to lower replenishment, and stains are generated due to the reduction of sulfite, and in severe cases, precipitation of sulfur and silver sulfide occurs. The problem is that the mixing ratio of the color developing solution becomes high, the desilvering property is lowered, and crystal precipitation easily occurs on the wall or edge of the bleach-fixing bath.

For the purpose of improving the stability of the bleach-fixing solution, a patent for a carbonyl bisulfite adduct has been filed (Japanese Patent Laid-Open Nos. 48-42733 and 50-5).
No. 1326, No. 56-107244, JP-A-1-26
7540, JP-A-3-233451). However, with the above technique, the stability of the bleach-fix solution is insufficiently improved,
Remarkably low replenishment of 20 to 150 ml per 1 m ^{2 of the} light-sensitive material was not always possible. In particular, p
The problem is that the stability of the bleaching replenisher with a low H content is insufficient, and if the concentration of preservatives such as sulfites and carbonyl bisulfite adducts is increased, desilvering properties are reduced and crystal precipitation easily occurs. Occurs. In recent years, there is no technology that can significantly reduce the replenishment amount even when the processing amount is small and the residence time is long in the mini-lab which has been introduced to the market, and new technological development was needed.

[0004]

Therefore, the first aspect of the present invention
The object of (1) is to provide a processing method in which the stability of the bleach-fixing solution is improved and the replenishment amount is remarkably reduced. Also, the second
Is to provide a processing method having good desilvering property. A third object is to reduce crystal precipitation in the processor tank.

[0005]

As a result of studying the above-mentioned problems, the present inventors have found that the object can be achieved by the following processing method. (1) In a method in which an exposed silver halide color photographic light-sensitive material is treated with a color developing solution and then with a bleach-fixing solution, the bleach-fixing solution is Fe of a compound represented by the following general formula (I). (III) A method for processing a silver halide color photographic light-sensitive material, which contains a complex salt and is replenished in a bleach-fixing bath in an amount of 20 to 150 ml per 1 m ^{2 of the} light-sensitive material. General formula (I)

[0006]

[Chemical 2]

(2) The treatment method according to (I), wherein the [S, S] form is selectively used among the optical isomers of the compound of the general formula (I). (3) The processing method according to (1), wherein the bleach-fix replenisher has a pH of 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 consisting of silver chloride (1)
The processing method described.

The present invention will be described in detail below. First, the bleach-fixing solution of the present invention will be described in detail below. The compound represented by formula (I) is 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 and has a carbon number of Those of 1 to 10 are preferable. An alkyl group is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable. 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, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is more preferable. The aliphatic group and 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 groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-methylphenyl), amino groups (eg dimethylamino), acylamino groups (Eg acetylamino),
Sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), 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 Groups, aryloxycarbonyl groups (eg phenyloxycarbonyl), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl), acyloxy groups (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 above 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, 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 different even in the same straight-chain or branched having 2 to 8 carbon atoms Alkylene group (eg, ethylene, propylene), cycloalkylene group having 5 to 10 carbon atoms (eg, 1,2-cyclohexyl), arylene group having 6 to 10 carbon atoms (eg, o-phenylene), aralkylene having 7 to 10 carbon atoms Represents a group (for example, 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 (eg, methyl) or an aryl group having 6 to 10 carbon atoms (eg, phenyl) which may be substituted with. M _a , M _b , M _c and M _d each represent a hydrogen atom or a cation. Examples of the cation include alkali metals (eg, lithium, sodium, potassium), ammonium (eg, ammonium, tetraethylammonium), pyridinium and the like. The linking group represented by W may have a substituent, and as the substituent, those exemplified as the substituents of R ₁ to R ₆ can be applied. The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the heteroatom is nitrogen, and more preferably a group such as an imidazolyl group linked to W ¹ and W ^{2 by} a carbon atom 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, and m is 2
Alternatively, when it is 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 the following.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metal (eg, lithium, sodium, potassium) ammonium (eg, ammonium and tetraethylammonium) and pyridinium. .

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 thereto.

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

The compound represented by the general formula (I) may be any optical isomer. [S, S] body, [S, S
It may be an R] -form, a [R, S] -form, a [R, R] -form, or a mixture of these isomers. For example,
The isomers of Exemplified Compound (I-1) include the [S, S] -form, [S, R] -form and [R,
It may be the R] form or a mixture of these isomers. Further, 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] form among the optical isomers, such as exemplified compound (I-1). In addition, compounds synthesized from L-amino acid as a raw material are preferable. The [S, S] form is also preferable because it is easily biodegraded. Here, “selective” means that 70% or more of the mixture of optical isomers is [S,
S] form, and more preferably 90% or more is occupied by [S, S] form. The compound represented by the general formula (I) of the present invention can be synthesized according to the description of JP-A-63-199295, JP-A-3-173857 and the like. These documents relate to a detergent composition using a compound represented by the general formula (I) of the present invention as a chelating agent, and its Fe (III) complex salt is bleached for a silver halide color photographic light-sensitive material. It is not described that it is effective as a drug. In addition, the method of selective synthesis of [S, S] isomers was performed by UMEZAWA et al. In THE JOURNAL OF ANTIBIOT
It can be easily synthesized by the method described in ICS, Vol, XXXVII, No.4, pp426 (APR. 1984) and the like. Next, specific examples of the Fe (III) complex salt used in the present invention are shown below, but the present invention is not limited thereto.

[0021]

[Chemical 11]

[0022]

[Chemical 12]

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 replenishing solution used in processing.
The ferric complex salt used in the bleach-fixing solution may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and ferric salt (for example, ferric sulfate, ferric chloride) may be added. Ferrous iron,
A complex salt may be formed in the bleach-fixing solution by coexisting with ferric bromide, iron (III) nitrate, ammonium iron (III) sulfate, etc.). The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is generally preferably in the range of 0.01 to 10%.

The compound forming the ferric complex salt in the bleach-fixing solution (composition) of the present invention is preferably 50 mol% or more of the compound represented by the general formula (I) described above, and It is preferable to occupy 80 mol% or more.
In the present invention, as the compound forming the ferric complex salt in the bleach-fixing solution, the compound represented by the above general formula (I) may be used alone or in combination of two or more kinds. Good. Further, within the scope of the present invention, as the compound forming the ferric complex salt in the bleach-fixing solution, a compound other than the compound represented by the 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 oxidant may be used in combination as the bleaching agent in addition to the above-mentioned ferric iron complex salt as long as 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-fixing solution of the present invention is 0.005 to 0.5 mol /
The range of liter is suitable, the range of 0.01 to 0.25 mol / liter is preferable, and the range of 0.0 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 / liter, more preferably 0.01 to 1.
It is 0 mol / liter.

Next, the desilvering process applicable to the present invention will be described. In the present invention, the desilvering step includes a bleach-fixing step, and includes a bleach-fixing step, a bleach-bleach-fixing step, a bleach-fixing step-fixing step, a bleaching step-bleach-fixing step-fixing step and the like. In the present invention, the bleach-fixing step alone is preferable in terms of simplifying and speeding up the desilvering step.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, Japanese Patent Laid-Open No. 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.
No. 53-32735, U.S. Pat. No. 3,706,561 and the like, and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

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

The bleach-fixing solution or the fixing agent used in 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 solubilizers such as thioureas,
These can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing 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, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5.
It is in the range of up to 1.0 mol.

The bleach-fixing solution and fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) and metas as preservatives. It preferably contains a sulfite ion-releasing compound such as bisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are about 0.02 ~
The content is preferably 0.05 mol / liter, more preferably 0.04 to 0.40 mol / liter.

As a preservative for the bleach-fixing solution and the fixing solution,
Although sulfite is generally added, ascorbic acid, carbonyl bisulfite adduct, carbonyl compound, or the like may be added, and benzenesulfinic acids are also effective. Furthermore, a buffer for the bleach-fixing solution and the fixing solution,
A fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as necessary.

In the present invention, it is particularly preferable that the bleach-fixing solution does not substantially contain ammonium ions from the viewpoint of preventing precipitation and improving the adhesiveness of the light-sensitive material after processing. With substantially no ammonium ion,
0.05 mol / liter or less, 0.05
It is more preferably not more than mol / liter, and most preferably not contained at all. In the bleach-fixing solution of the present invention, the preferred pH range is 3 to 10, and further 4
-9 are preferable. Among them, when a high silver chloride emulsion is used in the light-sensitive material, the pH of the bleach-fixing solution is preferably 7.0 to 4.0, particularly preferably 6.5 to 4.0. In addition, the replenishing amount to the bleach-fix bath is reduced to adjust the pH of the bleach-fix bath to 6.
The pH of the bleach-fixing replenisher needs to be further lowered to maintain it at 5 or less.
Particularly preferably, it is 5.5. So far, there has been a problem that the stability is poor when the pH of the bleach-fixing replenisher is set to 4.0 to 5.5. However, when the compound of the general formula (I) of the present invention is used as an iron complex salt, it is stable. The 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 became possible. The replenishing amount of the bleach-fixing bath of the present invention is 1 m ² of the light-sensitive material.
It is 20 to 150 ml per unit. Particularly preferred is 25 to 100 ml, and more preferred is 30 to 50 ml. The processing temperature of the bleach-fixing solution applicable to the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 10 seconds to 5 minutes, preferably 20 seconds to 2 minutes.

Next, the color developing solution 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 a p-phenylenediamine derivative, and as a representative example, 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 sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is generally about 4 to 50 millimoles per liter of the color developing solution, but the amount of the color developing replenisher is preferably about 1 liter of the replenisher. Is about 21 millimolar to 45 millimolar, more preferably about 23 millimolar to 40 millimolar.
It is a millimolar concentration. The method of the present invention is particularly effective for concentrated color developing replenishers.

In carrying out the present invention, in the work environment,
It is preferred to use a color developer which is substantially free of benzyl alcohol. The term "substantially free from" means preferably 2 ml / liter or less, more preferably
The benzyl alcohol concentration is 0.5 ml / liter or less, and most preferably, no benzyl alcohol is contained.

The color developing solution used in the present invention contains substantially no sulfite ion in order to suppress fluctuations in photographic characteristics due to continuous processing. X10 ^-3 mol / liter or less) is more preferable. Most preferably, it contains no sulfite ion at all. However, in the present invention, however, a very small amount of sulfite ion used for the antioxidant of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded.

The color developer used in the present invention preferably contains substantially no sulfite ion, but it further contains hydroxylamine in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine. Do not do (Here, "substantially free from" means a hydroxylamine concentration of 5.0 × 10 ^-3 mol / liter or less.)
Is more preferable. Most preferably, it contains no hydroxylamine at all.

The color developing solution used in the present invention more preferably contains an organic preservative in place of the hydroxylamine and sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyl. Ketones,
Organic preservatives in which α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. are particularly effective Is. These are disclosed in Japanese Examined Patent Publication No. 48-30496 and Japanese Unexamined Patent Publication No. 52-143020.
No. 63-4235, 63-30845, 63-21647, 63
-44655, 63-53551, 63-43140, 63-56654
63, 58-346, 63-43138, 63-146041, 63
63-44657, 63-44656, U.S. Pat.No. 3,615,503,
2,494,903, JP-A-1-97953, 1-186939,
No. 1-186940, No. 1-187557, No. 2-306244. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, JP-A-63-239447, and JP-A-63. −
128340, amines as described in JP-A 1-186939 and 1-187557, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, The aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be used if necessary. Especially alkanolamines such as triethanolamine, N, N-
Diethylhydroxylamine and 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 catechol-3,5-disulfonate. Is preferred.

In particular, it is more preferable to use the dialkylhydroxylamine and / or hydrazine derivative in combination with the alkanolamines from the viewpoint of improving the stability of the color developing solution, and thus improving the stability during continuous processing. .

In the present invention, chlorine ion is contained in the color developing solution.
3.0 x 10^-2~ 1.5 x 10^-1Must contain mol / liter
And are preferred. Particularly preferably 3.5 × 10^-2~ 1 x 10^-1
Mol / liter. Chloride concentration is 1.5 × 10^-1~
Ten^-1If it is more than mol / liter, it will delay the development.
It has disadvantages and is not preferable. Also 3.0 × 10^-2Mol / li
If it is less than torr, it is not preferable for preventing fog. Book
In the present invention, bromine ion was added to the color developer at 3.0 × 10
^-FiveMol / liter ~ 1.0 × 10^-3Contains mol / liter
It is preferable. More preferably 5.0 × 10 ^-Five~ 5 x 10
^-FourMol / liter. Bromine ion concentration is 1 × 10^-3Mo
If it is more than 1 liter / liter, the development will be delayed and the maximum density and
Sensitivity decreases to 3.0 × 10^-FiveLess than mol / liter
In this case, fog cannot be sufficiently prevented.

Here, the chlorine ion and the bromine ion may be directly added to the color developing solution or may be eluted from the light-sensitive material to the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance 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 developing solution. As a source of bromide ions,
Examples thereof include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When eluted from the light-sensitive material during the development processing, chlorine ions and bromine ions may be supplied together from the emulsion,
It may be supplied from a source other than the emulsion.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution may further contain a compound of a known developing solution component. it can. In order to maintain the above pH,
It is preferable to use various buffers. As the buffering agent, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt,
Leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane Salts, lysine salts and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or higher,
It is particularly preferable to use these buffers because they have the advantages of being inexpensive and having no adverse effect on the photographic performance (fogging, etc.) even when added to the color developer.

Specific examples of these 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, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developer is preferably 0.1 mol / liter or more, and particularly preferably 0.1 mol / liter to 0.4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing precipitation of calcium or magnesium, or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, trans-silohexanediaminetetraacetic 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. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution.
For example, it is about 0.1 to 10 g per liter.

If desired, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37-1
No. 6088, No. 37-5987, No. 38-7826, No. 44-12380,
Thioether compounds represented by U.S. Pat. No. 45-9019 and U.S. Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-1.
A p-phenylenediamine compound represented by 5554,
JP-A-50-137726, JP-B-44-30074, JP-A-56-15
Quaternary ammonium salts represented by 6826 and 52-43429, US Pat. Nos. 2,494,903, 3,128,182, and US Pat.
4,230,796, 3,253,919, Japanese Patent Publication No. 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,
42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat. No. 3,532,501, and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added if necessary. The benzyl alcohol is as described above.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, 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, 2 Typical examples are 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, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4
/ Liter. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, polyalkyleneimine and the like may be added.

The processing temperature of the color developer applicable to the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. Processing time
20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably small, but 20 to 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, preferably 30 to 200 ml, more preferably
It is 30 ml to 150 ml. Next, the washing and / or stabilizing step used in the present invention will be described.

In the present invention, washing and / or stabilization treatment is carried out after desilvering treatment such as fixing or bleach-fixing. The replenishing amount in the water washing step or the stabilizing step is 3 to 50 times, preferably 3 to 30 times, the amount carried in from the previous bath per unit area of the light-sensitive material. It is more preferably 3 to 10 times. When the stabilization treatment is performed after washing with water, the method of the present invention is effective in a treatment system in which the stabilization step of the final step is 3 to 50 times. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by reducing the overflow of washing water into a bleach-fixing bath, which is the pre-bath, by replenishing the bleach-fixing bath with a concentrated liquid by reducing the overflow of washing water by a multi-stage countercurrent system. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set to a range. Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 0.5 liter to 1 per 1 m ^{2 of the} light-sensitive material.
Although it can be less than or equal to 1 liter, due to the increase in the residence time of water in the tank, bacteria are propagated, and the floating substances produced 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, the isothiazolone compounds and siabendazoles described in JP-A-57-8542, 61-1201
Chlorinated bactericides such as chlorinated sodium isocyanurate described in No. 45, benzotriazole described in JP-A No. 61-267761, copper ions and others Hiroshi Horiguchi "Bacterial antifungal chemistry"
(1986) Sankyo Publishing, edited by Sanitary Technology Society, "Microbial sterilization, sterilization, and fungicide technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal "Encyclopedia of Antibacterial and Antifungal Agents" (1986) It is also possible to use the bactericide described in. Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softening agent can be used.

It is also possible to carry out treatment with the stabilizing solution directly after the above washing step or without going 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 buffering agent for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surface active agent, an optical brightening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without passing through a water washing step, known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like are used. , All can be used.
In addition, it is also a preferred 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 for the washing step or stabilizing step is 4
It is -10, more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the light-sensitive material, but generally 15 to
45 ° C, preferably 20-40 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. It is preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds.

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

The material of the replenishing cartridge for filling the processing liquid used in the present invention may be any material such as paper, plastic, metal, etc., and particularly has an oxygen permeability coefficient of 50 ml / (m ² · atm · day). ) The following plastic materials are preferred. In addition, the oxygen permeability coefficient is "O ₂ permeation of plastic container" (O ₂ permeation of plastic conta).
iner, Modern Packing; NJCalyan, 1968) 12
It can be measured by the method described in pages 143 to 145 of the monthly issue. Specific preferred plastic materials 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, for the purpose of reducing oxygen permeability, PVDC, NY, P
The use of E, EVA, EVAL and PET is preferred. These materials may be used alone and may be molded and used, or a method of forming a film and laminating a plurality of kinds (so-called composite film) may be used. Further, as the shape of the container, various types such as bottle type, cubic type, pillow type and the like can be used, but the present invention is a cubic type which is flexible and easy to handle and can be reduced in volume after use and Structures similar to are particularly preferred. When used as a composite film, the structures shown below are particularly preferable, but 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 internal volume of the completed container is about 100 ml to 20 liter, preferably about 500 ml to 10 liter. The container (cartridge) may have a cardboard or a plastic outer box, or may be integrally formed with the outer box. Various processing liquids can be filled in the cartridge of the present invention. For example, color developing solution, black and white developing solution, bleaching solution, adjusting solution, reversing solution, fixing solution,
Although a bleach-fixing solution, a stabilizing solution and the like can be mentioned, it is particularly preferable to use a color developing solution, a black-and-white developing solution, a fixing solution and a bleach-fixing solution for a cartridge having a low oxygen permeability coefficient.

Next, the photosensitive material usable 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 arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are The following patent publications, particularly European Patent EP 0,355,660A2 (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 of which silver chloride is 90 mol% or more.
An emulsion in which 95 to 99.9 mol% or more, and more preferably 98 to 99.9 mol% or more of silver chloride is preferably used, and chlorobromide in which all layers are composed of 98 to 99.9 mol% or more of silver chloride A silver emulsion is particularly preferable. The coated silver amount 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-based cyan couplers described in 33144, the 3-hydroxypyridine-based cyan couplers described in European Patent EP0,333,185A2 (among others, the 4-equivalent couplers of the couplers (42) listed as specific examples are chlorine). Two equivalents with a leaving group or coupler (6)
And (9) are particularly preferable) and the cyclic active methylene cyan couplers described in JP-A 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used. .

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving the sharpness of an image. Dye (among others, oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohol (dihydric alcohol) ( For example, it is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with trimethylolethane or the like. Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that 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. Preferably.

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

The term "photographic layer" as used herein refers to a laminated hydrophilic colloid group layer containing at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling. 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. And can be adjusted by changing the aging condition. 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide 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 are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacyl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds.

Examples of the color light-sensitive material used in the present invention include color paper, color reversal paper, direct positive color light-sensitive material, color negative film and color reversal film. A color sensitive material for printing such as color paper is preferable. The support used in the light-sensitive material according to the present invention may be a support provided on a support having a silver halide emulsion layer on which a white polyester support or a layer containing a white pigment is provided for a display. You may use. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. Especially so that the display can be viewed with both reflected light and transmitted light,
It is preferable to set the transmission density of the support in the range of 0.35 to 0.8.

The light-sensitive 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, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0070]

EXAMPLES Next, the present invention will be specifically described 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 dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multi-layered color photographic paper was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (So
lv-3) and (Solv-7) (4.1 g) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution 185.
Emulsified dispersion A was prepared by emulsifying and dispersing in cc. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 of large size emulsion having average grain size 0.88 μm and small size emulsion of 0.70 μm)
Mixture (silver molar ratio). Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively, and silver bromide of each size emulsion is 0.
3 mol% localized on a part of the particle surface) was prepared.
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver of 2.0 ×, respectively.
10 ⁻⁴ mol, and 2.5 × 10 ⁻⁴ mol was added to each of the small-sized emulsions A. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.
The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer 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. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

In each layer, Cpd-10 and Cpd-11
Were 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 in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0075]

[Chemical 13]

(2.0 × 10 ⁻⁴ mol for large size emulsion A and 2.5 × 10 ⁻⁴ mol for small size emulsion A per mol of silver halide)

[0077]

[Chemical 14]

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion B and 5.6 × 10 ⁻⁴ mol for small size emulsion B), and

[0079]

[Chemical 15]

(7.0 × 10 ⁻⁵ mol for large size emulsion B and 1.0 × 10 ⁻⁵ mol for small size emulsion B per mol of silver halide)

[0081]

[Chemical 16]

(0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide)

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]

[Chemical 17]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 × 10 ^-5 moles, 7.7 × 10 ^-4 moles per mole,
2.5 × 10 ⁻⁴ mol was added.

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

Further, the following dyes (in parentheses represent the coating amount) were added to the emulsion layer to prevent irradiation.

[0088]

[Chemical 18]

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

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

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 Mixing Prevention Layer) Gelatin 0.64 Color mixing 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 with average grain size 0.55 μm and small size emulsion with 0.39 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and in each size emulsion, 0.8 mol% of AgBr is locally contained in a part of the grain surface.) 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 (UV Absorbing Layer) Gelatin 1.41 UV Absorbing Agent (UV-1) 0.47 Color Mixing Preventing Agent (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 average grain size 0.58 μm and small size emulsion 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain surface in each size emulsion.) 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 (UV Absorbing Layer) Gelatin 0.48 UV Absorbing Agent (UV-1) 0.16 Color Mixing Preventing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.10 Polyvinyl alcohol acryl-modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03

[0098]

[Chemical 19]

[0099]

[Chemical 20]

[0100]

[Chemical 21]

[0101]

[Chemical formula 22]

[0102]

[Chemical formula 23]

[0103]

[Chemical formula 24]

After imagewise exposing the above light-sensitive material, continuous processing (running test) was carried out in the following processing steps using a paper processor. The processing amount was 100 m ² of the light-sensitive material per week, and a running test was performed for 4 weeks. The bleach-fixing solution was tested by changing the replenishing amount, and the replenishing solutions A to E were used so that the iron complex salt concentration, the thiosulfate concentration and the pH were the same in the running equilibrium state. (Refer to Table 6) Processing process Temperature Time Replenishment amount ^* Tank capacity Color development 38.5 ℃ 45 seconds 73ml 5L Bleach fixing 35.0 ℃ 45 seconds See Table 6 5L Rinse (1) 35.0 ℃ 20sec-3L Rinse (2) 35.0 ° C 20 seconds −3 liters Rinse (3) 35.0 ° C 20 seconds −3 liters Rinse (4) 35.0 ° C 30 seconds 242 ml 3 liters * Replenishment amount per 1 m ^{2 of} photosensitive material (rinse is from (4) (4 tank countercurrent method to (1))

[0105]

[Table 6]

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [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 Optical brightener (WHITEX 4 Sumitomo Chemical Co., Ltd.) 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 Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline.3 / 2 Sulfuric acid / monohydrate 5.0 g 11.5 g Water was added to 1000 ml 1000 ml pH (at 25 ° C / potassium hydroxide and sulfuric acid 10.00 11.00

[Rinse Solution] (The same as the tank solution and the replenisher solution) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 The photosensitizer (Fuji Photo Film Co., Ltd.) Company made,
An FWH type, light source color temperature of 3200 ° K) was used and staircase wedge exposure was applied. The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 0.1 seconds.

After the running test was completed, the above samples were processed by the same automatic processor, and the desilvering property and stain were evaluated by the following methods. Desilvering property: The amount of silver remaining at the maximum density point of the sample was measured by a fluorescent X-ray analysis method. Stain: The yellow density in the unexposed area of the sample was measured using a Macbeth densitometer. Next, the sulfite ion concentration in the bleach-fix solution after the running test was analyzed by the iodometry method to evaluate the stability of the solution. The above results are summarized in Table 7.

[0109]

[Table 7]

As shown in Table 7, when the replenishing amount of the bleach-fixing solution is remarkably reduced to 150 to 30 ml per 1 m ^{2 of the} light-sensitive material, ethylenediaminetetraacetic acid which has been generally used in the past is used as a preservative. A certain sulfite ion concentration is extremely low, yellow stain is increased in the light-sensitive material after processing, and desilvering property is deteriorated. (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 property are exhibited, which shows the effect of the present invention. (Experiment No. 6,
(See 7, 8, 9, 10, 11, 12, 13 or 14)
Furthermore, No. 9, 1 using only the [S, S] form of (I-1)
In Nos. 0 and 11, especially, excellent performance in desilvering, suppression of increase in stain, and deterioration of sulfite is shown.

Example 2 The bleach-fixing tank liquid after the running test of Experiment Nos. 3 to 11 of Example 1 was 5 cm × 10 cm × 50 cm in internal dimensions.
Put 2 liters each into a PVC container of (depth), cover with a PVC float so that the area where the liquid comes into contact with air is 10 cm ^2, and place it in a thermostat at 40 ° C for 2 hours. Left for a week. 1 week and 2 weeks after leaving,
The sulfite ion concentration of each solution was measured by the same method as in Example-1, and the precipitate or turbidity in the solution was observed. The results are shown in Table 8.

[0112]

[Table 8]

As shown in Table 8, when the bleach-fix solution of Example-1 in which the processing amount per week was 100 m ² of the light-sensitive material was aged, it was found that ethylenediaminetetraacetic acid, which has been generally used conventionally, had a The sulfite ion, which is a preservative, almost disappeared in a week, the solution became cloudy, and a precipitate occurred in 2 weeks after the passage of time. This shows the situation when the processing amount was further reduced, and that small amount processing with a replenishing amount of the bleach-fixing solution of 150 to 30 ml / m ² was impossible in terms of stability. It is shown. However, when the compound of the present invention is used, even 2 weeks after aging,
The concentration of sulfite ion, which is a preservative, is sufficiently high, there is no turbidity of the solution, and it is in a good condition. It is possible to replenish the bleach-fixing solution of 150 to 30 ml / m ² and even a smaller processing amount is possible. It is shown.

Example 3 With the bleach-fix replenisher shown below, a aging test was conducted in the same manner as in Example-2. [Bleach-fixing replenisher] water 400 ml ammonium thiosulfate 176 ml ammonium sulfite 70 g chelating agent (see Table 9) 0.281 mol ferric nitrate 9 hydrate 0.264 mol nitric acid (67%) 53 g 1,000 ml pH (25 ° C / adjusted with nitric acid or ammonia) See Table 9

Each replenisher solution is 5 cm × 10 cm × 50 depth in inside dimension.
2 liters of each was placed in a polyvinyl chloride container of cm, and a polyvinyl chloride float was placed so that the area where the liquid came into contact with air was 20 cm ^2, and the container was left in a constant temperature bath at 40 ° C. for 4 weeks. Two and four weeks after the standing, the sulfite ion concentration of the solution was measured by the same method as in Example-2, and the precipitate or turbidity in the solution was observed. The results are shown in Table 9.

[0116]

[Table 9]

As shown in Table 9, ethylenediaminetetraacetic acid which has been generally used in the past has a very poor stability of sulfite ion at a pH of 5.5 or less, and precipitates or cloudiness occurs after 2 weeks. . However, when the compound of the present invention is used, the pH is in the range of 5.5 to 4.0.
The stability is almost the same as 6.0, and it is possible to lower the pH of the replenisher necessary for lowering the content of the bleach-fixing solution. Among the present invention, the pH of the replenisher is 4.0 to 4.0.
It turns out that it is more preferable that it is 5.5.

Example 4 A multilayer color photographic paper having the following layer structure was prepared on a paper support whose both surfaces were laminated with polyethylene and whose surface was subjected to corona discharge treatment. The coating liquid was prepared as follows.

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

The following were used as the spectral sensitizing dye for each layer. Blue-sensitive emulsion layer: anhydro-5,5'-dichloro-3,
3'-Disulfoethylthiacyanine 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-Neopentyl thiadicarbocyanine iodide

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

The following materials were used as the anti-irradiation dye. [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-disulfonate anthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy -4- (3- (3-cyano-5-oxo-1- (4-sulfonatephenyl)-
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 the coating amount in terms of silver.

Support A paper support laminated on both sides with polyethylene and the surface of which has been subjected to corona discharge treatment.

First Layer (Blue Sensitive Layer) The above-mentioned silver chlorobromide emulsion (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 Mixing Prevention Layer) Gelatin 0.80 Color mixing inhibitor (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 (0.7 mol% of AgBr, cubic, average grain 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 Mixing Prevention Layer) Gelatin 1.70 Color mixing inhibitor (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 above-mentioned silver chlorobromide emulsion (AgBr 4 mol%, cubic, average grain 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 accelerator (Cpd-5) 0.15

Sixth Layer (UV Absorbing Layer) Gelatin 0.70 UV Absorbing Agent (UV-1) 0.26 UV 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)
Butylamido] 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) Antifading agent

[0135]

[Chemical 25]

(Cpd-2) Color mixing inhibitor 2,5-di-tert-octylhydroquinone (Cpd-3) Color fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2 , 2'-Spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color development accelerator p- (p-toluenesulnamido) phenyl-dodecane

(Solv-1) Solvent Di (2-ethylhexyl) phthalate (Solv-2) Solvent Dibutylphthalate (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 to light by the method described in Example 1 and imagewise exposed to the above-mentioned light-sensitive material separately. Using a paper processor, the tank volume of the bleach-fix solution was processed in the following processing steps. A continuous process (running test) was carried out until the replenishment was carried out twice as much as above, and then a color image was obtained.

Processing process Temperature Time Replenishment amount ^* Tank capacity Color development 40 ° C 45 seconds 35 ml 7 liters Bleach fixing 30-36 ° C 45 seconds 30 ml 7 liters Stable 1 30-37 ° C 20 seconds-4 liters Stable 2 30 〜37 ℃ 20 seconds -4 liters Stable 3 30-37 ℃ 20 seconds -4 liters Stable 4 30-37 ℃ 30 seconds 120ml 4 liters Dry 70-85 ℃ 60 seconds * Replenishment amount per 1m ^{2 of} photosensitive material (stable (4 tank counter current system from 4 to 1)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [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 Whitening agent (4,4'-diaminostilbene type) 2.0 g 6.0 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 12.50

[Bleach-fixing solution] Tank solution Replenishing solution 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 nitric acid No. 1 2 Iron nonahydrate 0.13 mol 0.26 mol Nitric acid (67%) 30 g 50 g Water added 1000 ml 1000 ml pH (25 ° C) 6.0 4.6

[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 Water was added to 1000 ml pH (25 ° C) 4.0 Running test From the start to the end, good desilvering property, good white background, good bleach-fixing solution Good results were shown without crystal precipitation in the liquid or processor.

Example 5 Even when the compound (I-1) was replaced by an equimolar amount of (I-5), (I-9) or (I-12) in Example 4, good desilvering was simultaneously achieved. You can get sex.

[0145]

According to the present invention, the stability of the bleach-fixing solution is improved, and the processing in which the replenishing amount is remarkably reduced becomes possible. In particular, when the pH of the replenisher was lowered to 4.0 to 5.5, the stability was improved and good treatment became possible. Also, good desilvering property could be obtained. Further, the compound used in the present invention has optical isomers, among which [S. When the S] form is mainly used, it is possible to obtain excellent effects such as improvement of desilvering property, suppression of stain, and stabilization of sulfite ion.

Claims (4)

[Claims] 1. A method of treating 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). A method of processing a silver halide color photographic light-sensitive material, which comprises a compound Fe (III) complex salt and is replenished to a bleach-fixing bath in an amount of 20 to 150 ml per 1 m ^{2 of the} light-sensitive material. 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 is a divalent linking group containing a carbon atom. Represents M ₁ ,
M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) 2. The processing method according to claim 1, wherein the [S, S] form is selectively used among the optical isomers of the compound of the general formula (I). 3. The pH of the bleach-fixing replenisher is 4.0 to 5.5.
The processing method according to claim 1, wherein 4. The silver halide color photographic light-sensitive material comprises 9
The processing method according to claim 1, further comprising at least one emulsion layer containing light-sensitive silver halide grains having 0 mol% or more of silver chloride.