JP3052227B2 - 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, and more particularly to a method for processing a silver halide color photographic light-sensitive material capable of performing rapid processing.

[0002]

2. Description of the Related Art Generally, processing of a silver halide photographic light-sensitive material comprises a developing step and a silver removing step. In the processing of color light-sensitive materials, in the silver removal process, the developed silver generated in the color development process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing effect, and soluble silver is formed together with unused silver halide. The fixing agent is removed from the photosensitive layer.
(Fixing) Bleaching and fixing may be performed as independent bleaching steps and fixing steps, respectively, or may be performed simultaneously as bleach-fixing steps. Details of these processing steps can be found in James, “The Theory of Photographic Pro
cess "4'th edition) (1977). The above-mentioned processing steps are generally performed by an automatic developing machine. In particular, in recent years, a small automatic developing machine called a mini lab has been sold in stores. The mini-lab has a large work load, such as preparation of a processing solution and recovery of waste liquid, and is expected to reduce the amount of processing solution used, that is, to reduce the amount of replenishment. It is rare.
Against this background, in particular, there has been a strong demand for speeding-up and low replenishment of the processing steps, and significant speeding-up and low replenishment of the bleaching step, fixing step or bleach-fixing step has been desired.

In the fixing step, most thiosulfate compounds have been used as a fixing agent, but various other fixing agents have been studied. For example, JP-A-4-
Nos. 143755 and 4-143756 describe mesoionic compounds, and Heist, "Modern Photographic Processing," Vol. 2 (Haist, "MODERN PHOTOGR
APHIC PROCESSING "vol.2 (1979) p.580-
On page 584, compounds such as 3,6-dithia-1,8-octanediol, ethylene-bis (thioglycolic acid) and thiocyanic acid are described as fixing agents or fixing accelerators.

[0004] However, none of these methods was satisfactory in fixing speed, poor in solubility, or had safety problems, and could not be put to practical use. In particular, when the replenishment amount of the fixing solution is reduced, the fixing speed is reduced due to the influence of silver ions and halogen ions eluted from the light-sensitive material, and it is difficult to achieve both low replenishment and quickness. there were. Also, if the fixing agent is used at a high concentration, the discoloration of the yellow dye becomes large when the processed photographic material is stored for a long period of time, which is not preferable. Therefore, an object of the present invention is to provide a processing method which is quick and has good image storability.

[0005]

The above object has been achieved by the following processing method. In the method of processing a silver halide photographic light-sensitive material with a processing solution having a fixing ability, the dry film thickness of all the constituent layers except the support and the undercoat layer and the back layer on the support is 12 to 20 μm. A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing solution having a fixing ability contains at least one compound represented by the following general formula (I). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group or a heterocyclic group, and M represents a hydrogen atom or a cationic group.)

The dry film thickness of the photosensitive material, that is, the dry film thickness of all the constituent layers except the support and the undercoat layer and the back layer of the support is 12.0 to 20.0 μm. More preferably 1
2.0 to 17.0 μm.

[0007] The thickness of the photosensitive material to be measured is 2
The photosensitive material was stored under conditions of 5 ° C. and 50% RH for 7 days after the preparation, and firstly the total thickness of the photosensitive material was measured, and then the thickness of the coating layer on the support was removed and the thickness was measured again. The difference is used to determine the thickness of the entire coating layer excluding the support of the photosensitive material. The measurement of the thickness is performed, for example, by using a contact-type thick-electric conversion element to measure the thickness (Anritus Electric Co.
Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite. Also,
Using a scanning electron microscope, a cross-sectional photograph of the photosensitive material is taken (preferably at a magnification of 3,000 or more), and the total thickness on the support can be measured.

In the present invention, the swelling ratio of the photosensitive material [｛(2
5 ° C., equilibrium swelling thickness in H ₂ O—25 ° C., 55% RH
Dry film thickness at 25 ° C. and 55% RH｝ × 100] is preferably 50 to 200%, and 70 to 1%.
50% is more preferred. When the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and photographic performance,
This has an adverse effect on image quality such as desilvering properties and film physical properties such as film strength. Further, the film swelling speed of the light-sensitive material in the present invention is defined as 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds) is defined as a saturated swelling film thickness. When the time required to reach the film thickness of No. 2 is defined as the swelling speed T1 / 2, T1 / 2 is preferably 15 seconds or less. More preferably, it is 9 seconds or less.

Next, the general formula (I) of the present invention will be described in detail. In the general formula (I), the aliphatic group represented by R is
It preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl, alkenyl, alkynyl or aralkyl group having 1 to 20 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include, for example, methyl group, ethyl group, isopropyl group, t-
Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl And the like.

In the general formula (I), the aromatic group represented by R preferably has 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms. For example, a phenyl group and a naphthyl group.

In the general formula (I), the heterocyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. is there. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, such as a pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, and phenyl group. , A furyl group, a benzthiazolyl group, and the like.

In the general formula (I), each group represented by R may be substituted. Examples of the substituent include the following.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc., alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group, etc.), alkynyl Group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic group ( For example, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc., alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 2-naphthyloxy group, etc.) ), Amino groups (eg, unsubstituted amino groups, dimethylamino groups, ethylamino groups, anilino groups, etc.), Shiruamino group (e.g., acetylamino group, benzoylamino group, etc.), a ureido group (e.g., unsubstituted ureido group, N- methylureido group, N-
Phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group) , N, N-
Dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfonyl group (eg, mesyl group, A sulfinyl group (eg, a methylsulfinyl group, a phenylsulfinyl group, etc.), an alkyloxycarbonyl group (eg, a methoxycarbonyl group,
Ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), acyl group (eg, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.), acyloxy group (eg, acetoxy group, benzoyloxy group, etc.) ), A phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), a cyano group,
Examples include a sulfo group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (eg, a trimethylammonio group), a phosphonio group, a hydrazino group, and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), examples of the cationic group represented by M include an alkali metal ion (eg, sodium ion, potassium ion, lithium ion, cesium ion) and an alkaline earth metal ion (eg, calcium ion, magnesium ion) Ion), an ammonium group (eg, an unsubstituted ammonium group, a methylammonium group, a trimethylammonium group, a tetramethylammonium group, a dimethylbenzylammonium group), and a guanidinium group.

In the general formula (I), more preferably, R
Represents an aliphatic group or a heterocyclic group, and M represents a hydrogen atom, an alkali metal ion or an ammonium group.

Still more preferably, in the general formula (I), R represents an aliphatic group having 1 to 6 carbon atoms, and M represents a sodium ion, a potassium ion or an unsubstituted ammonium group.

Most preferably, R in the general formula (I)
Represents an alkyl group having 1 to 6 carbon atoms, and M represents a sodium ion, a potassium ion or an unsubstituted ammonium group.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The compound represented by the general formula (I) can be synthesized by a reaction between a sulfonyl chloride compound and a sulfide such as an alkali metal sulfide or ammonium sulfide or a reaction between a sulfinic acid compound and elemental sulfur. ing.
For example, Journal of Analytical Chemistry (J. Anal. Chem. USSR), 20, 1701, (195)
0) and German Patent No. 840,693 (1952).

Although the compound of the present invention may be used alone,
When used in combination with a normal fixing agent, its performance can be more remarkably exhibited.

When the compound of the present invention is used alone, it is suitably added in an amount of 1 × 10 ^{−3 to} 5 mol / l per liter of a processing solution having a fixing ability (hereinafter also referred to as a fixing ability solution). And preferably 1 × 10 ^{−2 to} 3 mol / l, more preferably 1 × 10 ⁻¹ to 2 mol / l.

The compounds of the present invention may be used in combination with other fixing agents. Examples of the fixing agent used in combination include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates (rodane salts) such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate;
And thiourea compounds, thioether compounds, mercapto compounds, mesoionic compounds and the like. Of these, thiosulfates are preferred. The preferable addition amount of the thiosulfate is 0.1 to 3 mol, more preferably 0.5 to 1.5 mol, per liter of the fixing solution.

When the compound of the present invention is used in combination with a thiosulfate, the amount of the compound of the present invention is preferably 0.01 to 3 mol, more preferably 0.05 to 1 mol per liter of the fixing solution.
２2 mol, most preferably 0.1-1 mol. When the added amount is small, the effect of promoting fixing becomes small, and
If the amount is too large, precipitation during the low-temperature storage of the fixing solution tends to occur.

When the compound of the present invention is used in combination with a thiosulfate, the fixing performance is remarkably improved, particularly when silver ions and halogen ions (particularly iodine ions) accumulate when the fixing solution is treated with a small replenishing amount. It is. Here, when the fixing agent used in combination is sodium thiosulfate, M in the general formula (I) is preferably a sodium ion, and when the fixing agent used in combination is ammonium thiosulfate, M in the general formula (I) is an unsubstituted ammonium group. Is preferred.

The present invention relates to a solution having a fixing ability containing the compound represented by formula (I) and having a dry film thickness of 12 to
It processes a photosensitive material having a thickness of 20 μm. Under this condition, the fixing speed is high and the fade of the yellow dye of the processed photosensitive material is small. If the dry film thickness is more than this, fixing is delayed and yellow dye fading increases. Also, 12μ
When the photosensitive material is less than m, sufficient sensitivity cannot be imparted to the photosensitive material, and the use of the compound of the formula (I) results in a small improvement in fixing speed, and the remarkable effect of the invention cannot be seen.

The processing solution having fixing ability of the present invention specifically refers to a fixing solution, a bleach-fixing solution, a fixing stabilizing solution, etc.
Preferred are a fixer and a bleach-fixer. The fixing solution contains a fixing agent. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate; thiocyanates (rodane salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; Urea, thioether and the like can be mentioned. Of these, thiosulfates are preferred. A preferred amount of the thiosulfate is 0.1 to 3 mol, preferably 0.5 to 1.5 mol, per liter of the fixing solution.

The compound of the general formula (I) of the present invention is used together with the above fixing agent to promote fixing. In particular, when silver ions and halogen ions (particularly iodine ions) accumulate when the fixing solution is processed at a low replenishing rate, the fixing promoting effect is remarkable. In particular, when the dry film thickness of the photosensitive material is within the range of the present invention, the effect of promoting the fixing is large. The present invention is particularly effective when the concentration of alkali metal ions in the fixing solution is 0.5 to 8 g ions / liter. More preferably, it is 1 to 6 gram ions / liter, particularly preferably 1.5 to 4 gram ions / liter. Further, even when the concentration of ammonium ion in the fixing solution is low, the effect becomes remarkable, and preferably 1 g ion / liter or less.
Particularly preferably, it is 0.5 g ion / liter or less, most preferably 0.1 g ion / liter or less. The preferred use amount of the compound of the general formula (I) is
0.01 to 3 mol per liter, particularly preferably 0.1 to 0.3 mol per liter.
The amount is from 0.5 to 2 mol, most preferably from 0.1 to 0.5 mol. Further, a fixing accelerator or a fixing agent other than the present invention, for example, ammonium thiocyanate (rhodanammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) may be used in combination. The amount of these compounds used together is 0.1 to 1 liter of the fixing solution.
It is good to use it in an amount of from 01 to 1 mol, preferably from 0.1 to 0.5 mol.

In the fixing solution, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg, sodium acetaldehyde bisulfite) or preservatives are used as preservatives. A sulfinic acid compound described in Japanese Unexamined Patent Publication No. 1-231051 can be contained. Furthermore, various fluorescent whitening agents, defoamers or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.

Further, it is preferable to add various chelating agents such as aminopolycarboxylic acids and organic phosphonic acids to the fixing solution for the purpose of stabilizing the processing solution. Preferred chelating agents include nitrilotriacetic acid, hydroxyethyliminodiacetic acid, nitriloacetic acid dipropionic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, And aminopolycarboxylic acids such as 3,3-propylenediamine disuccinic acid. The chelating agent is added in an amount of 0.01 to 0.3 mol, preferably 0.03 to 0.3 mol per liter of the treatment liquid.
0.2 mol.

In the present invention, the bleach-fixing process may be performed before or after the fixing process. The bleach-fixing solution can contain compounds that can be contained in the fixing solution and the bleaching solution described below.

Bleaching-fixing solution at the start of processing (starting solution)
Is prepared by dissolving the compound used in the above-mentioned bleach-fixing solution in water, but may be prepared by mixing separately prepared bleaching solution and fixing solution in appropriate amounts.

The pH of the fixing solution for a color light-sensitive material is preferably from 5 to 9, and more preferably from 6 to 7.5. In the bleach-fix solution, 5.5 to 8.0 is preferable, and 6.0 to 7.5 is more preferable.

In order to adjust the fixing solution or the bleach-fixing solution to such a pH range, and as a buffer, pKa is 6.0 to 6.0.
It is preferable to contain the compound in the range of 9.0 to improve the stability of the processing solution. These compounds include:
For example, phosphates or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned. , Most preferred are imidazole compounds. Preferred examples of the imidazole compound are the compounds represented by the general formula (I) in JP-A-4-130432, and specific examples are the imidazole compounds (1) to (12) in the same specification. Of these, particularly preferred are imidazole and 2-methylimidazole. These compounds are preferably used in an amount of 0.01 to 2 mol, preferably 0.05 mol to 0.1 mol, per liter of the processing solution.
5 moles.

In addition to the replenishment of the fixer replenisher, it is preferable that washing water or a stabilizing solution for the post-bath is introduced into the fixer. In this case, part or all of the overflow of the processing solution in the post-bath may be introduced into the fixing bath, or the processing solution in the processing bath may be directly sent to the fixing bath by a pump. When the replenishment method is employed, the total replenishment amount of the fixing solution (including washing water and a stabilizing solution when introduced into the fixing bath, including the amount thereof) is 100 to 2000 m per m ² of the photosensitive material.
1 is preferred, but more preferably 100 to 800 ml. The effect of the present invention becomes remarkable as the replenishment amount becomes lower.

In the present invention, the total processing time of the processing having a fixing ability is 0.5 to 4 minutes, preferably 0.5 to 2 minutes.
Minutes, particularly preferably 0.5 to 1 minute. In the present invention, the total processing time of the desilvering step comprising a combination of bleaching, bleach-fixing and fixing is preferably from 45 seconds to 4 minutes, more preferably from 1 minute to 2 minutes. The processing temperature is 25 to 50.
° C, preferably 35 to 45 ° C.

Silver can be recovered from the fixing solution of the present invention by a known method, and a regenerating solution subjected to such silver recovery can be used. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, and German Patent No. 2,331,220), and an ion exchange method. (JP-A-51-17114, German Patent No. 2,548,237) and a metal substitution method (UK Patent No. 1,353,805) are effective. These silver recovery methods are preferably performed in-line from the tank liquid because the rapid processing suitability is further improved.

After the fixing process, a washing process is usually performed. After the treatment with the fixing solution, a simple processing method in which the stabilization treatment using a stabilizing solution is performed without substantially washing with water may be used.

The light-sensitive material according to the present invention is prepared according to the RD.
No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881, can be used for development processing. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methylaniline. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
β-methoxyethylaniline, 4-amino-3-methyl-N-
Methyl-N- (3-hydroxypropyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N -Ethyl-N
-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline,
4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-methyl-N-
Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3
-Methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2
-Methylpropyl) aniline, 4-amino-3-methyl-N, N
-Bis (4-hydroxybutyl) aniline, 4-amino-3-
Methyl-N, N-bis (5-hydroxypentyl) aniline,
4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-
Hydroxybutyl) aniline, 4-amino-3-methoxy-N
-Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-
3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl)
Examples include aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably from 0.0002 mol to 0.2 mol, more preferably from 0.001 mol to 1 mol per liter of the color developer.
0.1 mol.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphate 5-sulfosalicylates, chlorides, bromides, iodides, benzimidazoles, It generally contains a development inhibitor such as a thiazole or a mercapto compound or an antifoggant. If necessary, hydroxylamine and diethylhydroxylamine may be used.
No. 144446, hydroxylamines represented by the general formula (I), sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples. . Of the above,
As the preservative, a substituted hydroxylamine is most preferable, and among them, a compound having an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group, or a hydroxyl group as a substituent is preferable. Most preferred examples are N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salts. As the chelating agent, a compound having biodegradability is preferable. An example of this is disclosed in
JP-A-3-146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-2677751
JP-A-2-229146, JP-A-3-18684
No. 1, German patent 3739610, European patent 468325
And the like can be mentioned. It is preferable that the processing solution in the replenishing tank or processing tank of the color developing solution be shielded with a liquid agent such as a high boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developing solution in the present invention is from 20 to 55C, preferably from 30 to 55C. The processing time is 20 seconds to 5 minutes, preferably 3 seconds for the photographic material.
0 second to 3 minutes and 20 seconds. More preferably, 1 minute to 2 minutes 3
0 seconds, and 10 seconds to 1 minute 2 for printing materials.
0 seconds, preferably 10 seconds to 60 seconds, more preferably 10 seconds to 40 seconds.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid,
Bleaching agents, such as iron complex salts of 1,3-propylenediaminetetraacetate, from the lower right column of the fourth page to the upper left column of the fifth page; carbamoyl-based bleaching agents described in JP-A-4-73647; A bleaching agent, a bleaching agent having a heterocyclic ring described in JP-A-4-174432, a bleaching agent described in European Patent Publication No. 520457, including a ferric N- (2-carboxyphenyl) iminodiacetic acid complex salt; Japanese Patent Application No. 3-252775 including ferric acetic acid ethylenediamine-N-2-carboxyphenyl-N, N ', N'-triacetate
A bleaching agent described in EP-A-501479, a bleaching agent described in JP-A-4-127145,
Ferric aminopolycarboxylic acid salts described in page (11) of JP-A-3-144446 or salts thereof are preferably used. The organic aminocarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

These bleaching treatments are preferably carried out immediately after color development, but in the case of reversal treatments, they are generally carried out via an adjusting bath (a bleaching accelerating bath may be used). These adjustment baths may contain an image stabilizer described below. In the present invention, the desilvering bath contains, in addition to the bleaching agent, (1) described in JP-A-3-144446 described above.
2) Rehalogenating agents, pH buffers and known additives, aminopolycarboxylic acids, organic phosphonic acids and the like described on page 2 can be used. In the present invention, various bleaching accelerators can be added to the bleaching solution or its pre-bath. Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858 and German Patents 1,2.
90,821, British Patent 1,138,842
No., JP-A-53-95630, Research
Compounds having a mercapto group or disulfide group described in Disclosure No. 17129 (July, 1978), thiazolidine derivatives described in JP-A-50-140129, and described in US Pat. No. 3,706,561 Thiourea derivative of JP-A-58-16235
Iodides, German Patent 2,748,43
The polyethylene oxides described in the specification of JP-A No. 0, the polyamine compound described in JP-B-45-8836, and the like can be used. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferred are mercapto compounds described in British Patent No. 1,138,842 and JP-A-2-190856.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids have an acid dissociation constant (p
Ka) is a compound having 2 to 5.5, and a dibasic acid is particularly preferable. Organic acids are specifically monobasic acids, such as acetic acid,
Preferred are propionic acid, hydroxyacetic acid and the like, and more preferred dibasic acids include succinic acid, glutaric acid, maleic acid, fumaric acid, malonic acid, adipic acid and the like. Most preferred are succinic, glutaric and maleic acids.

The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Using Process C-41, 3rd Edition (1982), BL-1 to BL, issued by Eastman Kodak Company
Items described on page-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of JP-A-7 can be used as they are.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photographic material, and a method described in JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while making the emulsion surface contact with the wiper blade provided in the liquid, to make the emulsion surface turbulent, thereby increasing the stirring effect And a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. Automatic developing machines used for the photosensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258,
It is preferable to have a photosensitive material conveying means described in JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

Further, the processing solution having the bleaching ability of the present invention comprises:
The overflow liquid used for the treatment is recovered, and after the components are added to correct the composition, the overflow liquid can be reused. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990), page 39, issued by Fuji Photo Film Co., Ltd.
The matters described on page 40 are applicable. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder, and the hygroscopicity is low.
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electric field regeneration, a method for regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

The photographic material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage
e Society of MotionPicture and Television Engine
ers, Vol. 64, pp. 248-253 (May 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated floating substances adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition,
No. 57-8,542, Isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles. Published by Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Techniques" (1982).
) Can also be used.

Washing water in the processing of the light-sensitive material of the present invention
The pH is between 4 and 9, preferably between 5 and 8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, the application, etc.
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in Japanese Patent No. 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed photosensitive material. Among them, a nonionic surfactant is preferably used, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and the stabilizing solution preferably contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345,172A1 can be mentioned.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and the amount of water in the bleaching tank is replenished in proportion to the amount of evaporation.
The evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A Nos. 3-249644, 3-249645 and 3-249646 is preferable.
Tap water may be used as the water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The various processing solutions in the present invention are used at 10 ° C. to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

The light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer, JP-A-61-43748, 59-113
No. 438, 59-113440, 61-20037, couplers as described in the specification of 61-20038, DIR compounds and the like may be contained. May be included. The plurality of silver halide emulsion layers constituting each unit light-sensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in JP-A-06543 and the like, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokuaki Akira
As described in JP-A-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738, 62-63936
As described in the specification, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, a medium-speed emulsion in the same color-sensitive layer from the side away from the support is used. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, U.S. Patent Nos. 4,663,271 and 4,705,7
No. 44, No. 4,707,436, JP-A Nos. 62-160448 and 63-160448
It is also preferable to dispose a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification of 89850, adjacent to or adjacent to the main photosensitive layer.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may have any silver halide composition. For example, silver chloride, silver bromide, silver chlorobromide,
Silver iodobromide, silver iodochloride or silver iodochlorobromide. In the case of a color photographic material for photography or a color reversal photographic material (for example, color negative film, reversal film, color reversal paper), silver iodobromide, silver iodochloride containing 0.1 to 30 mol% of silver iodide, Alternatively, silver iodochlorobromide is preferred. In particular, silver iodobromide containing 1 to 25 mol% of silver iodide is preferred. In the case of a direct positive color light-sensitive material, silver bromide or silver chlorobromide is preferred, and silver chloride is also preferred for rapid processing. In the case of a light-sensitive material for paper, silver chloride or silver chlorobromide is preferable, and in particular, silver chloride is 80 mol%.
The above, more preferably 95 mol% or more, most preferably 98 mol% or more of silver chlorobromide is preferable.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (197
Dec. 8), pp. 22-23, "I. Emulsionprep (Emulsionprep.
aration and types) ”and No. 18716 (November 1979
Mon.), p. 648, No. 307105 (November 1989), 863-865
Page and Grafkid "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique Phot)
ographique, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDuffin, Photogr)
aphic Emulsion Chemistry (Focal Press, 1966)), "Manufacture and Coating of Photographic Emulsions" by Zerikman et al., Published by Focal Press (VL Zelikman et al., Making and Coatin).
g Photographic Emulsion, Focal Press, 1964) can be used.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
No. 48, 4,439,520 and British Patent No. 2,112,157. In particular, it is preferable to use an emulsion having a tabularity (Tarbulity) of 50 to 25,000 as described in U.S. Pat. No. 5,183,727. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in JP-A-264740. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, etc.
0 nm is preferred, and 5 to 20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
They can be mixed and used in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface, U.S. Pat. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 9-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains having the inside of the grains fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The light-sensitive material of the present invention preferably contains colloidal silver as an antihalation layer between the support and the emulsion layer. As colloidal silver, JP-A-5-13
Thickness of 0.02 as described in US Pat.
It is preferable to use colloidal silver having a size of not more than μm. The colloidal silver preferably has an edge length of at least twice the thickness thereof, an average edge length of 0.04 μm or less, and a thickness of 0.005 to 0.02 μm.
More preferably, the average edge length is 0.02 to 0.04 μm and the thickness is 0.005 to 0.012 μm. The coating amount of colloidal silver for the antihalation layer is 1 m
200 mg or less, more preferably 50 to 100 mg per ² is preferred. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives which can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer 〜page 649 right column 4. Brightening agent page 24 page 647 right column page 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7.Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Stat. 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound capable of reacting with formaldehyde described in US Pat. No. 4,411,987 or US Pat. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, International Publication WO88 / 04794, dyes dispersed by the method described in
EP 317,308A, U.S. Pat.No. 4,420,555, JP-A 1-2593
The dye described in No. 58 is preferably contained.

Various color couplers can be used in the color light-sensitive material applied to the processing according to the present invention. Specific examples thereof are RD No. 17643, VII-C described above.
To G, No. 307105, and VII-C to G, JP-A-62-215272, and JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
Nos. 69A and 482552A. As the yellow coupler, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
No. 3,973,968, U.S. Pat.
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patent Nos. 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, JP-A-1-213648 and the like. These can be used in combination unless the effects of the present invention are impaired.

Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179042, European Patent. Published No. 044796
An acylacetamide-based yellow coupler characterized by an acyl group described in No. 9 and a compound represented by the general formula (Cp-
2) Yellow coupler.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure Magazine No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure Magazine No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO 88/04795 are more preferable. Particularly preferred magenta couplers include pyrazoloazole-based magenta couplers of the general formula (I) in page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-135944. 5-pyrazolone magenta couplers of the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferred are the aforementioned pyrazoloazole-based magenta couplers.

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferred. Further, Japanese Unexamined Patent Application Publication No. 64-553
Nos. 64-554, 64-555, 64-5
No. 56, pyrazoloazole couplers described in EP-A-0,488,248 and EP-A-0,491,197.
, A pyrroloimidazole coupler described in European Patent Publication No. 0,456,226A, a pyrazolopyrimidine coupler described in JP-A-64-46753, U.S. Pat. No. 4,818,672.
, An imidazole coupler described in JP-A-2-33144, a pyrrolotriazine coupler described in JP-A-4-204730, a cyclic active methylene cyan coupler described in JP-A-64-32260, 183
Nos. 658, 2-262655 and 2-85851
And the couplers described in JP-A-3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are described in US Patents 3,451,820 and 4,08
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No. etc. U.S. Pat. No. 4,366,237 discloses a coupler in which a coloring dye has an appropriate diffusibility.
No. 2,125,570, EP 9
No. 6,570, West German Patent (Published) No. 3,234,533
Those described in the above item are preferred. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers which release a development inhibitor are described in the aforementioned RD Magazine No. 17643, Patents VII to F, JP-A-57-151944 and JP-A-57-15423.
No. 4, No. 60-184248, No. 63-37346
Nos. 4,248,962 and 4,782.
No. 012 is preferred. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,
No. 188, JP-A-59-157538 and JP-A-59-17.
No. 0840 is preferred.

Other couplers which can be used in the color photographic element of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,61
No. 8, etc .;
No. 50, No. 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI
R redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye that recolors after detachment, RD Magazine No. 11449, and the same magazine No. 2424
No. 1, bleach accelerator releasing couplers described in JP-A-61-201247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like, JP-A-63-75747.
And couplers releasing a fluorescent dye described in U.S. Pat. No. 4,774,181.

Typical amounts of couplers used are in the range of from 0.001 to 1 mol per mol of photosensitive silver halide;
Preferably, 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler,
For cyan couplers, the amount is 0.002 to 0.3 mol.

The coupler used in the present invention can be introduced into a photographic material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Esters of isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylase) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the light-sensitive material of the present invention, a dye preservability improving compound as described in European Patent EP 0,277,589 A2 can be used together with a coupler. It is particularly preferable when used in combination with a pyrazoloazole-based magenta coupler. Various color fading inhibitors can be used in combination in the light-sensitive material of the present invention. Examples of the organic fading inhibitor include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzene Kind,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated.

The light-sensitive material of the present invention comprises a hydroquinone derivative, an aminophenol derivative,
It may contain gallic acid derivatives, ascorbic acid derivatives and the like. Further, in order to prevent the cyan dye image from deteriorating due to heat and especially light, a benzotriazole-based ultraviolet absorber described in, for example, US Pat. No. 3,533,794 may be provided on the cyan coloring layer and on both adjacent layers. It is more effective to introduce The color light-sensitive material of the present invention includes phenethyl alcohol and JP-A-63-257747,
62-272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A-1-80941 It is preferable to add various preservatives or fungicides such as 2- and 4- (4-thiazolyl) benzimidazole.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Indoaniline compounds described in No. 42,597, No. 3,342,5
No. 99, Research Disclosure No. 14,850 and above
No. 15,159, Schiff base compounds, aldol compounds described in US Pat. No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are JP-A-56-64339 and JP-A-57-14454.
No. 7, and No. 58-115438.

Suitable supports that can be used in the light-sensitive material of the present invention are described, for example, in RD. No. 17643, page 28, No. 187
No.307105 of No.307105 from the right column of page 647 to the left column of page 648
It is described on page 879. As the material for the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used. Preferred are cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (eg, polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene naphthalate). Can be The film support used when the light-sensitive material of the present invention is used as a color negative film, a higher draining effect is obtained, and the mixing of the pre-bath component into the next step can be reduced, so that polyethylene terephthalate or Polyethylene naphthalate described in Functional Materials, February 1991, pages 20 to 28 is preferred. When the light-sensitive material of the present invention is used as a color negative film, the thickness of the support is preferably from 70 to 130 μm, particularly preferably 80 to 130 μm.
~ 120 µm is preferred.

In the case where the light-sensitive material of the present invention is used as a color negative film, the support is described in International Patent Publication WO90 /
04205, FIG. Those having the magnetic recording layer described in 1A are preferable. As described in JP-A-4-62543, the support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin or the like on one surface. Also, Japanese Patent Application Laid-Open No.
No. 4628 having a stripe magnetic recording layer and having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer can also be used. A protective layer described in JP-A-4-73737 can be provided on the magnetic recording layer.

In the case where the light-sensitive material of the present invention is used as a color negative film, the packaging (patrone) for accommodating the color negative film may be any of those currently used or known, and in particular, US Pat. No. 4,834,306.
No., FIG. 1 to FIG. 3 and US Pat. No. 4,846,418, FIG. 1 to FIG.
Those described in No. 3 are preferred.

The format of the color negative film used in the present invention is based on Japanese Industrial Standard "JIS.K-7519".
(1982) ", and
Any known format other than the format described in -287040 can be used. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

The light-sensitive material of the present invention is disclosed in JP-B-2-32615,
Even when applied to a film unit with a lens described in Japanese Utility Model Publication No. 3-39784 or the like, the effect is more easily exhibited and is effective.

The following are examples of automatic developing machines capable of performing the processing of the present invention. FP560BAL, FP360BAL, FP90 manufactured by Fuji Photo Film
0AL, FP550B, FP350, FP230B, F
NCP900III, FNCCP600II, FNCP30
0. The details of the automatic developing machine (processor) are described in an attached manual, for example, an instruction manual (for an administrator / for an operator), a service manual, a parts list, and the like.

Next, the processing liquid container used in the present invention will be described. Conventional processing solution containers include high-density polyethylene (HDPE) and polyvinyl chloride resin (P
VC), polyethylene terephthalate (PET), etc.
A rigid container using a layer material or a multilayer material such as nylon / polyethylene (NY / PE) can be used. Also, after the contents are discharged and emptied, the volume of the container can be reduced, that is, a flexible liquid container that can easily reduce the required space can be used. In the present invention, it is preferable to use a container having the above flexibility. As a specific example of the flexible container, a liquid container that is opened and closed by a lid member that engages with a hard mouth protruding upward from the flexible container body,
A container in which the container body and the mouth are integrally formed, and which has a bellows portion in at least a part of the height of the container body (FIG. 1)
Can be given.

Hereinafter, the flexible container having the bellows portion will be described. The container shape has a bellows portion, and its horizontal cross section includes a square shape, for example, a substantially square shape (FIG. 1), a substantially hexagonal shape, a substantially octagonal shape, a round shape (FIG. 2), an elliptical shape, and the like. A substantially square shape or a substantially hexagonal shape is preferable in that the required space in the presence of the contents is reduced. The number of the bellows portions (irregular portions) is preferably 2 to 20, more preferably 3 to 10, and particularly preferably 4 to 8 convex portions. There is no particular limitation on the degree of the unevenness of the bellows portion, but the outer circumferential dimension of the concave portion is 85% or less, preferably 40 to 75%, more preferably 50 to 75% of the outer circumferential size of the convex portion. The ratio of the total height of the container body in which the bellows portion is completely compressed to the total height of the container body before the bellows portion is compressed is preferably 50% or less, more preferably 40% or less, and particularly preferably 10 to 3%.
0%. This ratio is preferably 10% or more in terms of manufacturing and design.

The liquid container can have a necessary gas barrier property by changing the material and the material used. For example, when a high oxygen barrier property is required as in a developer or the like, a low density polyethylene / polyvinyl alcohol ethylene copolymer / low density polyethylene (LD
PE / EVOH / LDPE) or a low-density polyethylene / nylon (LDPE / NY) layer-based multilayer structure such as a low-density polyethylene / nylon (LDPE / NY) layer structure, and has a gas barrier property of 25 ml / m ^2. day ・ atm (20 ℃
65%) or less, preferably 0.5 to 10 ml / m ² · day
atm (20 ° C., 65%).
For example, when oxygen barrier properties are not necessarily required, such as a bleaching solution, it can be formed using low-density polyethylene (LDPE) alone or ethylene-vinyl acetate copolymer resin (EVA). Here, the low-density polyethylene has a density of 0.940 g / cc or less, preferably 0.1 g / cc or less.
90 to 0.94 g / cc, more preferably 0.905 to 0.95 g / cc
0.925 g / cc can be used. In this case, the gas barrier property is 50 ml / m ² · day · atm (20 ° C 6
5%) or more, for example, 100 to 5000 ml / m ² · day · at
m (20 ° C. 65%).

The average thickness of the container mouth, the flange and the vicinity thereof is preferably 1 to 4 mm, more preferably 1 to 4 mm.
3 mm, particularly preferably 1.2 to 2.5 mm, the thickness of the container body is preferably 0.1 to 1.5
mm, more preferably 0.2 to 1.0 mm, particularly preferably 0.3 to 0.7 mm, and the difference between the two is preferably 0.2 mm, more preferably about 0.5 mm. To be. The ratio of the surface area (cm ² ) of the container to the internal volume (cm ³ ) of the container is increased by the bellows structure, but is preferably 0.3 to 1.5 cm ⁻¹ , more preferably 0.4 to 1.2 cm ⁻¹ .
cm ^-1, it is particularly preferably 0.5 to 1.0 cm ^-1.
When filling the above-mentioned container with the liquid, it is preferable that the head space (the space in the upper part of the container where there is no processing liquid) is small from the viewpoint of improving the liquid stability. Liquid overflows easily.
The liquid filling rate in the container is preferably 65 to 95%, more preferably 70 to 90%.

It is preferable that the cap or inner plug of the container is formed of the same material as that of the container main body, in that the selection of the used container for recycling is easy. By changing the material and the raw material, a necessary gas barrier property can be provided in the same manner as the main body described above. The inner volume of the container is not particularly limited, but is preferably 50 ml to 5 liters from the viewpoint of handleability.

The above container can be recycled by the following method. 1. At the user's site, shrink the bellows of the used container, cover it with a stopper, and store it. 2. When the quantity reaches a certain level at the user, it is collected from the user. 3. With the cap on, the used container is hung on a shredder device and cut into predetermined dimensions. 4. The cut pieces are put into a water tank, washed for a predetermined time, dried, and used as a molding material for a resin product. 5. The regenerated material can be mixed with a virgin material to form the above-described container, and a processing liquid can be newly filled to produce a product. Hereinafter, specific examples of the flexible processing solution containers A and B having a bellows portion will be described.

Container name Container A Container B Type shape Roughly square (FIG. 1) Rough circle (FIG. 2) Outer circumference of convex part of bellows (cm) 24 cm 24 cm Outer circumference of concave part of bellows part (cm) 16 cm 16 cm Outer circumference of concave part / Convex circumference (%) 67% 67% Height before shrinking bellows (cm) 18cm 18cm Height after shrinking bellows (cm) 4cm 4cm Decrease in height due to shrinkage of bellows 22% 22% Contents (ml) 580ml 580ml Filling amount (ml) 500ml 500ml Filling rate (%) 86% 86% Container body material LDPE (density 0.91g / cc) LDPE (density 0.91g / cc) / EVOH / LDPE (density 0.91 g / cc) cap, the inner plug material undefined undefined oxygen permeability ^{(ml / m 2 · day ·} atm (20 ℃ 65%)) 100 1.0 thickness of the main body (mm) 0.5 0.5 container surface area (cm ²⁾ 520 505

[0099]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Preparation of silver platelets with thickness up to about 0.02 μm for antihalation layer

3.488 kg of distilled water was added to 112 g of gelatin.
Was heated at about 50 ° C. to dissolve the gelatin, and 4.0 g of calcium acetate and 2.0 g of potassium borohydride were added thereto. 6.0 dissolved immediately thereafter.
1 liter of an aqueous silver nitrate solution per liter was added with rapid stirring. Next, distilled water was added so that the final weight was 5.0 kg. The resulting product was cooled to near the gelation temperature and passed through a smaller hole into cooled water to form fine noodles.

A solution prepared by adding 6.5 g of potassium hydroquinone monosulfonate and 0.29 g of KCl to 81 g of distilled water was added to 650 g of reduced silver borohydride nuclei. The noodle slurry was cooled to about 6 ° C.

Sodium sulfite 11 was added to 122 g of distilled water.
A solution a in which 9.5 g and 0.98 g of sodium bisulfite were dissolved, and a solution b in which 9.75 g of silver nitrate was dissolved in 122 g of distilled water were prepared. Solution a and solution b were mixed and stirred to form a white precipitate (soluble silver salt), which was then immediately added to the noodle slurry with rapid stirring. Amplification proceeded at a temperature of 10 ° C. for about 80 minutes until all soluble silver salts were reduced on the nuclei. The obtained blue slurry particles were washed with tap water for about 30 minutes in a nylon mesh pack to desalinate. Water was drained until the weight of the product was 412 g, so that the blue silver dispersed and washed in the gel slurry became a silver dispersion having a concentration of 1.5% by weight upon melting.

The shape of the thus obtained colloidal silver (colloidal silver A) was confirmed by a transmission electron microscope, and was found to be a flat plate having an edge length of about 0.02 to 0.03 μm and a thickness of about 0.007 μm. It was silver particles.

On a subbed cellulose triacetate film support, there was prepared a sample 101 which was a multilayer color photographic material comprising each layer having the following composition. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin hardener ExS: amount sensitizing dye coating amount which represents the amount for silver halide and colloidal silver were represented in units of g / m ² of silver and coupler, for additives and gelatin in the unit of g / m ² , And the sensitizing dye was represented by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Colloidal silver A 0.08 Gelatin 1.3 ExM-1 2.0 × 10 ^-2 HBS-1 3.0 × 10 ^-2

Second layer (intermediate layer) Gelatin 1.4 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 HBS-2 7.0 × 10 ^-2

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.15 silver iodobromide emulsion B silver 0.25 gelatin 1.0 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS- 3 1.0 × 10 ^-5 ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 × 10 ^-2 ExC-7 1.0 × 10 ^-2 HBS-1 7.0 × 10 ^-3

Fourth layer (medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C silver 0.25 silver iodobromide emulsion D silver 0.45 gelatin 1.4 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS- 3 1.0 × 10 ^-5 ExC-1 0.16 ExC-2 8.0 × 10 ^-2 ExC-3 0.17 ExC-7 1.5 × 10 ^-2 ExY-1 2.0 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 HBS-1 0.10

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.60 gelatin 1.1 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC- 5 7.0 × 10 ^-2 ExC-6 8.0 × 10 ^-2 ExC-7 1.5 × 10 ^-2 HBS-1 0.15 HBS-2 8.0 × 10 ^-2

Sixth layer (intermediate layer) Gelatin 0.75 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 HBS-1 5.0 × 10 ^-2

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F silver 0.10 silver iodobromide emulsion G silver 0.15 gelatin 0.40 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS- 6 0.3 × 10 ^-4 ExM-1 3.0 × 10 ^-2 ExM-2 0.20 ExY-1 3.0 × 10 ^-2 Cpd-11 7.0 × 10 ^-3 HBS-1 0.20

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.55 Gelatin 0.70 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM- 1 3.0 × 10 ^-2 ExM-2 0.25 ExM-3 1.5 × 10 ^-2 ExY-1 4.0 × 10 ^-2 Cpd-11 9.0 × 10 ^-3 HBS-1 0.20

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 0.45 Gelatin 0.60 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS- 7 3.0 × 10 ^-4 ExM-1 1.0 × 10 ^-2 ExM-4 3.9 × 10 ^-2 ExM-5 2.6 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 Cpd-9 2.0 × 10 ^-4 Cpd-10 2.0 × 10 ^-4 HBS-1 0.20 HBS-2 5.0 × 10 ^-2

Tenth layer (yellow filter layer) Gelatin 0.60 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 HBS-1 0.15

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J silver 0.10 silver iodobromide emulsion K silver 0.20 gelatin 0.70 ExS-8 2.0 × 10 ^-4 ExY-1 9.0 × 10 ^-2 ExY- 3 0.90 Cpd-2 1.0 × 10 ^-2 HBS-1 0.30

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L silver 0.40 gelatin 0.45 ExS-8 1.0 × 10 ^-4 ExY-3 0.12 Cpd-2 1.0 × 10 ^-3 HBS-1 4.0 × 10 ^-2

Thirteenth layer (first protective layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%)
0.20 Gelatin 0.60 UV-2 0.10 UV-3 0.10 UV-4 0.20 HBS-3 4.0 × 10 ^-2 P-3 9.0 × 10 ^-2

14th layer (second protective layer) Gelatin 0.65 B-1 (1.5 μm in diameter) 0.10 B-2 (1.5 μm in diameter) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40

Furthermore, storage stability, processability, pressure resistance, fungicide resistance,
The following Cpd-3, Cpd-5 to Cpd-8, P-
1, P-2, W-1 to W-3 were added. In addition to the above, B-4, F-1 to F-11, iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts are appropriately contained in each layer. Next, a list of the emulsions used in the present invention and the chemical structural formulas or chemical names of the compounds are shown below.

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[Table 1]

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[Table 2]

In Tables 1 and 2, (1) Each emulsion was subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-19938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-2-34090. I have. (3) For preparing tabular grains, low molecular weight gelatin was used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-2-237450 are observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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The amount of silver applied to Sample 101 was 3.98 g / m ² ,
The dry film thickness was 15 μm, the film swelling speed T _1/2 was 7 seconds, and the film swelling ratio was 140%. Also, the amount of gelatin in each layer,
Each of the samples 102 to 108 shown in Table A by adjusting the amount of silver applied.
Was prepared.

The sample 101 was cut to a width of 35 mm and photographed with a camera, and the following treatment was carried out for 15 days, 1 m ² per day. (Running processing) Each processing was performed by an automatic processor FP-5 manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using 60B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.6 ° C 15 ml 17 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C -5 liter Fixing (2) 50 seconds 38.0 ° C 5 ml 5 liter Washing water 30 seconds 38.0 ° C 12 ml 3.5 liter Stable (1) 20 seconds 38.0 ° C − 3 liter Stable (2) 20 seconds 38.0 ° C 15 ml 3 liter Drying 1 minute 30 60 ° C per second * The replenishment rate is 35 mm of photosensitive material and 1.1 m width (24E
x. The stabilizing solution and the fixing solution are countercurrent systems from (2) to (1).
All the overflow of the washing water was introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, 2.0 ml, 2.0 ml
Milliliters. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. The opening area of the above processor is 120 with color developer.
cm ^2, the bleaching solution in 120cm ^2, other processing solutions about 100
It was cm ^2.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.2 2.2 Disodium catechol-3,5-disulfonate 0.3 0.3 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.5 Carbonic acid Potassium 37.5 39.0 N, N-bis (2-sulfoethyl) hydroxylamine disodium 2.0 2.0 Potassium bromide 1.4-Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.6 2-Methyl-4- [N-ethyl-N- (Β-hydroxyethyl) amino] Aniline sulfate 4.5 6.8 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.21

(Bleaching solution) Tank solution (g) Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Glutaric acid 93 140 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.6 4.2

(Fixing (1) Tank Liquid) A mixture of the bleaching tank liquid and the following fixing tank liquid in a ratio of 15 to 85 (volume ratio). (PH 7.0) (Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 1957 Aqueous ammonium thiosulfate solution (700 g / liter) 280 ml 840 ml imidazole 15 45 Fixing accelerator (described in Table A) 0.3 mol 0.9 Mol Ethylenediaminetetraacetic acid 15 45 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.4 7.45

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 1,2-benzoisothiazoline-3- ON 0.05 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-Triazole 1.3 1,4-Bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 L pH 8.5

In the above-mentioned running process, each replenisher is prepared using a kit prepared in advance and filled in a container as follows (concentration kit is also available). At the end of each refill tank.

(Color developing solution) Part A: hydroxylamine sulfate 9.9 g Addition of amphoteric water 250 ml, pH 4.1 Part B: diethylenetriaminepentaacetic acid 6.05 g Catechol-3,5-disulfonate disodium 0.825 g 1-hydroxyethylidene- 1,1-diphosphonic acid 5.5 g sodium sulfite 15.1 g potassium carbonate 107.3 g N, N-bis (2-sulfoethyl) hydroxylamine disodium 5.5 g 2-methyl-4- [ethyl-N- (β-hydroxyethyl) amino] Aniline sulfate 18.7 g Both-ion exchanged water is added and 2.5 liters pH (adjusted with potassium hydroxide) 10.55 Liquid preparation method After adding three A parts, add three B parts. (Bleaching solution), (Fixing solution) Each replenisher as it is (solution kit) (Stable solution) 40 times concentrated solution of stabilizer Solution preparation method Add one stabilizer kit to 10 liters of water.

Container Color developing solution Bleaching solution / Fixing solution Stabilizing solution A part B part Shape substantially circular approximately square type substantially square type substantially circular shape Contents 290 ml 2.8 l 2.2 liter 290 ml Filling amount 250 ml 2.5 liter 2.0 liter 250ml container body material^* LDPE LDPE / EVOH / LDPE LDPE LDPE * Density 0.91g / cc Other material of cap and inner plug, high due to bellows shrinkage
The rate of decrease, oxygen permeability, and wall thickness
For the container B described in the sentence and the substantially square type, refer to the description in the text.
Same as vessel A. If the surface area of the container is almost circular,
300cm^Two, 2100cm for a roughly square type ^TwoIt is.

After completion of each running process, samples 101 to 101
Each of the samples 108 was exposed to light through a continuous wedge and processed to evaluate fixability and fading. The evaluation method is shown below. Fixability The amount of residual silver in the unexposed areas of the sample after the treatment was measured by X-ray fluorescence analysis. Fading property The decrease in density due to storage for 20 days at a temperature of 60 ° C. and a relative humidity of 75% in a portion having a yellow density of 2.0 was measured. Table 3 shows the results
It was shown to.

[0149]

[Table 3]

As can be seen from Table A, the sample using the fixing accelerator of the present invention and having a dry film thickness of 20 μm or less has good fixability and fading.

Example 2 Instead of the undercoated cellulose triacetate film support used for sample 101 prepared in Example 1, a
A sample 201 was prepared in the same manner as in Example 1 except that a polyethylene naphthalate of 0 μm was used as a support, and the back surface was coated with a stripe magnetic recording layer described in Example 1 of JP-A-4-124628. Produced. When a test similar to that of Example 1 was performed using this sample 201, the effect of the present invention was obtained as in Example 1. Further, instead of the support used for the sample 101 of Example 1,
The support and the backing layer were replaced with the same sample No. I-3 in Example 1 of JP-A-4-62543, and
C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK for protective layer
Was prepared in the same manner as in Example 1 except that was applied so as to be 15 mg / m ² . This sample 202 was processed into the format shown in FIG. 5 of JP-A-4-62543, and the same test as in Example 1 was performed.
The effect of the present invention was obtained in the same manner as described above.

Example 3 After the completion of the running process of process No. 3 in Example 1, the following color negative film was processed and found to be good without any stain. Real Photo Lot No. 87004 manufactured by Fuji Photo Film Co., Ltd. 〃 Super G100 S06214 〃 Super G400 V06252 〃 Photograph 800 M02-508 〃 Super HG1600 761004 〃 FUJICOLOR 160S 084016 (NSP-120-12) Example 4 The replenisher of the color developing solution was used as a concentration kit having the following three parts and left at room temperature for 6 months.
When the same treatment as in the treatment 3 of Example 1 was performed using the prepared replenisher, similar results were obtained. Part A Diethylenetriaminepentaacetic acid 14 g Catechol-3,5-disulfonate disodium 3.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 20 g Sodium sulfite 53 g N, N-bis (2-sulfoethyl) hydroxylamine disodium 20 g Carbonic acid Potassium 390 g Add both ion exchanged water and add 1000 ml pH (adjusted with potassium hydroxide) 13.8 Part B Diethylenetriaminepentaacetic acid 0.8 g hydroxylamine sulfate 36 g Add both ion exchanged water and add 500 ml pH (adjusted with potassium hydroxide) 3.5) Part C 2-Methyl-4- [N-ethyl-N-([beta] hydroxyethyl) amino] aniline sulfate 68 g Sodium sulfite 2.0 g Addition of both ion-exchanged water to 500 ml pH 2.2 Incidentally, the vessel was used below. Part A = Container A (filling amount 500 ml) Part B = Container A (〃) Part C = Container B (〃) Replenishment liquid preparation method Two parts A (1 liter), one part B in 8 liters of water (500 ml) and one part C (500 ml) are sequentially added and stirred well. In this way, 10 liters of the replenisher is prepared.

[0153]

The silver halide color photographic light-sensitive material has a dry film thickness of 12 to 20 .mu.m and is treated with a fixing solution containing a thiosulfonic acid compound. Stability can be improved.

[Brief description of the drawings]

FIG. 1 is a front view of a substantially rectangular container having a bellows portion for a flexible processing liquid.

FIG. 2 is a front view of a substantially round container having a bellows portion for a flexible processing liquid.

[Explanation of symbols]

 1 Kip 2 Inner plug 3 Mouth 4 Bellows

Claims (1)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material with a processing solution having a fixing ability, wherein a dry thickness of a support of the light-sensitive material and all constituent layers excluding an undercoat layer and a back layer on the support. Wherein the processing solution having a fixing ability contains at least one of the compounds represented by the following general formula (I). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group or a heterocyclic group, and M represents a hydrogen atom or a cationic group.)