JP2994543B2 - Photo-fixing composition and processing method using the same - 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 of processing a silver halide photographic light-sensitive material, and more particularly to a method of processing a silver halide photographic light-sensitive material which does not delay fixing even when the replenishment is reduced. is there.

[0002]

2. Description of the Related Art Generally, processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. Silver generated by development is oxidized by a bleaching agent and then dissolved by a fixing agent. A ferric (III) ion complex salt (for example, aminopolycarboxylic acid-iron (III) complex salt) is mainly used as a bleaching agent, and a thiosulfate is generally used as a fixing agent. On the other hand, the processing of a black-and-white photographic light-sensitive material comprises a developing step and a step of removing unexposed silver halide, and unlike the processing of a color photographic light-sensitive material, fixing processing is performed without a bleaching step after development. Also in this case, thiosulfate is usually used as a fixing agent.

In recent years, reduction of the replenishment amount of a photographic processing solution has been actively studied. The same applies to a bath having a fixing ability. However, silver ions and halogen ions (eg, iodine ions, bromine ions, and chloride ions) that accumulate in the running fatigue fluid as the replenishment rate decreases.
It is a major problem that the amount of the toner increases and the progress of fixing becomes slower, and there is a demand for a liquid composition that does not delay fixing even when the replenishment is reduced. In addition, when the replenishment rate is reduced, the residence time of the liquid is extended, so that the liquid stability also becomes a problem. Particularly, thiosulfate, which is widely used as a fixing agent, has a problem of sulfurization, and therefore, improvement of this point is highly desired.

In order to improve this point, thiocyanate ions (eg, ammonium thiocyanate, sodium thiocyanate) have conventionally been added to the fixing bath. Due to concerns about the effects of acid ions on the environment,
Good materials were desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which does not delay fixing even when the replenishment is reduced.
A second object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having excellent solution stability without causing precipitation even when the replenishment is reduced.

[0006]

The above object has been achieved by the following processing method and processing composition for a silver halide photographic material. (1) A photographic fixing ability composition comprising at least one compound represented by the following general formula (I). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a hydrogen atom or a cationic group.) (2) At least one layer of light on a support In a processing method in which a silver halide photographic light-sensitive material having a water-soluble silver halide emulsion layer is exposed to light and then developed, the bath having a fixing ability comprises at least one of the compounds represented by the general formula (I) described in (1). A method for processing a silver halide photographic light-sensitive material, characterized by comprising: (3) The silver halide photographic light-sensitive material according to (2), wherein the bath having a fixing ability contains at least one of the compounds represented by formula (I) in an amount of 0.01 mol / L or more. Processing method. (4) The silver halide photographic light-sensitive material according to (2), wherein the bath having a fixing ability contains thiosulfate ions and further contains at least one of the compounds represented by the general formula (I). Material treatment method. (5) The bath having a fixing ability contains not less than 0.1 mol / l of thiosulfate ions and at least 0.01 mol / l of the compound represented by the general formula (I). A method for processing a silver halide photographic light-sensitive material according to item (2). (6) In a processing method in which a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is exposed and then developed, the bath having a fixing ability is represented by the general formula described in (1). A method for processing a silver halide photographic light-sensitive material, which comprises at least one of the compounds represented by formula (I) and is further processed in a washing bath and / or stabilizing bath after processing having a fixing ability. (7) A photographic fixing power composition comprising at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a hydrogen atom or a cationic group.) General formula (II) R′SO ₂ M ′ (In the formula, R 'represents an aliphatic group, an aromatic group or a heterocyclic group, and M' represents a hydrogen atom or a cationic group.) (8) At least one photosensitive silver halide emulsion layer on a support In a processing method of exposing and developing a silver halide photographic light-sensitive material having the formula (I), a bath having a fixing ability comprises at least one of the compounds represented by the formula (I) described in the item (1) and a compound represented by the formula (II) A method for processing a silver halide photographic light-sensitive material, characterized by containing at least one compound represented by the formula: (9) The bath having a fixing ability contains thiosulfate ions, and at least one of the compounds represented by the general formula (I) described in (7) and at least one of the compounds represented by the general formula (II) The method for processing a silver halide photographic light-sensitive material according to item (8), which comprises: (10) At least one of the compound represented by the general formula (I) described in the item (7) and at least one of the compound represented by the general formula (II) are separately added at the time of preparing a replenisher having fixing ability. And / or a solution in which both are added is prepared. (11) The bath having fixing ability is prepared by adding at least one of the compounds represented by the general formula (I) described in (7) to 0.01
(8) The method for processing a silver halide photographic light-sensitive material as described in (8) above, wherein at least one of the compounds represented by the general formula (II) is contained in an amount of 0.01 mol / L or more. (12) The bath having a fixing ability contains thiosulfate ions in an amount of 0.1 mol / l or more, and further contains at least one of the compounds represented by the general formula (I) described in (7) in 0.01%.
(8) The method for processing a silver halide photographic light-sensitive material as described in (8) above, wherein at least one of the compounds represented by the general formula (II) is contained in an amount of 0.01 mol / L or more. (13) After exposing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support,
In the developing method, the bath having a fixing ability contains at least one compound represented by the general formula (I) described in the item (7) and at least one compound represented by the general formula (II); A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed in a washing bath and / or a stabilizing bath after the processing using a bath having a fixing ability.

Next, the general formulas (I) and (II) of the present invention will be described in detail. In the general formulas (I) and (II), the aliphatic group represented by R or R 'preferably has 1 carbon atom.
To 30 and, particularly, a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Alkyl group, alkenyl group,
Examples of the alkynyl group and the aralkyl group include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and an allyl group. , 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl and the like.

In the general formulas (I) and (II), R or R '
The aromatic group represented by is preferably an aromatic group having 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms, such as a phenyl group and a naphthyl group.

In the general formulas (I) and (II), R or 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. 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, for example, a pyridyl group, an imidazolyl group,
Quinolyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolinyl, thiazolyl, thienyl, furyl, benzothiazolyl and the like.

In the general formulas (I) and (II), each group represented by R or R 'may have a substituent.
Examples of the substituent include the following.

A halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, 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 thiosulfonic acid group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (for example, 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 formulas (I) and (II), M or M '
As the cation group represented by, an alkali metal ion (eg, sodium ion, potassium ion, lithium ion, cesium ion), an alkaline earth metal ion (eg, calcium ion, magnesium ion),
Examples include an ammonium group (for example, an unsubstituted ammonium group, a methyl ammonium group, a trimethyl ammonium group, a tetramethyl ammonium group, a dimethyl benzyl ammonium group), a guanidinium group, and the like.

In formula (I), R is preferably an aliphatic group, an aromatic group or a heterocyclic group, and M represents a hydrogen atom, an alkali metal ion or an ammonium group. 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, in the general formula (I), R represents an alkyl group having 1 to 6 carbon atoms, and M represents a sodium ion, a potassium ion or an unsubstituted ammonium group.

In the general formula (II), R 'is preferably an aliphatic group or an aromatic group, and M' is a hydrogen atom, an alkali metal ion or an ammonium group. General formula (I
In I), more preferably, R 'represents an aliphatic group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and M' represents a sodium ion, a potassium ion or an unsubstituted ammonium group. In formula (II), R ′ is most preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms substituted with at least one of a carboxy group, a sulfo group, a hydroxy group and an amino group. Represent,
M ′ represents a sodium ion, a potassium ion or an unsubstituted ammonium group.

The following are specific examples of the compounds of the general formulas (I) and (II) of the present invention, but the compounds of the present invention are not limited thereto.

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[0018]

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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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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. I have. For example, Journal of Analytical Chemistry (J. Anal. Chem. USSR), Volume 20, 1701 (1
950), German Patent No. 840,693 (1952)
Can be synthesized with reference to the above. The compound represented by the general formula (II) is generally synthesized by reduction of a sulfonyl chloride compound. As the reducing agent, zinc powder, sulfite ion, alkali metal sulfide and the like are used. Other methods are also known. Further, as described above, the compound of the general formula (II) is also used as a synthetic intermediate of the compound of the general formula (I). As a general method for synthesizing the compound of the general formula (II), for example, Chemical Review (Chem. Rev.
48, 69 (1951), Organic Synthesis, Collective Vol. I, 492.
(1941), Journal of American Chemical Society (J. Am. Chem. Soc.), 72, 1
215 (1950), ibid, 50, 792, 274
(1928).

The "bath having a fixing ability" in the present invention includes, for example, a fixing bath and a bleach-fixing bath, and various combinations are possible depending on the processing process. Examples of the photographic fixing ability composition in the present invention include those used in a fixing bath such as a fixing solution and those used in a bleach-fixing bath such as a bleach-fixing solution. The compounds of the formulas (I) and (II) of the present invention may be used alone or in combination, but when used in combination with a usual fixing agent, the performance can be more remarkably exhibited. The general formulas (I) and (I) of the present invention
The amount of the compound (I) used in the fixing bath or the bleach-fixing bath is preferably 1 × 10 ^{−3 to} 5 mol / l,
More preferably 1 × 10 ^{-2 to} 3 mol / l,
Particularly preferred is 1 × 10 ⁻¹ to 2 mol / l.
The abundance ratio of the general formulas (I) and (II) is arbitrary, but is preferably from 1: 9 to 9: 1, and more preferably from 2: 8 to 8: 2. The addition of the compounds of the formulas (I) and (II) of the present invention to a washing bath or a stabilizing bath, and the introduction of a photosensitive material from the previous bath are also effective in preventing precipitation in the washing bath or the stabilizing bath. Here, the concentration in these baths is 10 ^{−3 to} 0.
Five times is preferred.

The compounds of the general formulas (I) and (II) 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; Examples include urea compounds, thioether compounds, mercapto compounds, mesoionic compounds and the like. Of these, thiosulfates are preferred. The preferable addition amount of thiosulfate is 0.1 to 1 liter per fixer.
It is 3 moles, more preferably 0.3 to 1.5 moles. When the compounds of the general formulas (I) and (II) of the present invention are used in combination with a thiosulfate, the preferable addition amount of the compounds of the present invention is 0.01 to 3 mol per liter of fixing solution or bleach-fix bath, more preferably. Is 0.01 to 2 mol, most preferably 0.05 to 1 mol. If the amount is small, the effect of promoting the fixing and the effect of stabilizing the solution will be small. If the amount is too large, precipitation of the solution having the fixing ability during low-temperature storage tends to occur.

When the compounds of the general formulas (I) and (II) of the present invention are used in combination with a thiosulfate, silver ions and halogen ions (particularly iodine ion When () is accumulated, the fixing performance is remarkably improved. Here, when the fixing agent used in combination is sodium thiosulfate, M and M ′ in the general formulas (I) and (II) are preferably sodium ions, and when the fixing agent used in combination is ammonium thiosulfate, the general formula (I) M and M 'in (II) are preferably unsubstituted ammonium groups. When the compounds of the general formulas (I) and (II) of the present invention are added to a bath having a fixing ability, the replenisher may contain the general formulas (I) and (I)
The compounds of I) may be added separately, or a premixed solution may be added. As described above, since the compound of the general formula (I) can be synthesized using the compound of the general formula (II) as a raw material, especially when R and R ', M and M' in the general formulas (I) and (II) are the same. It is also possible to synthesize and add a mixture of the general formulas (I) and (II) in the compound synthesis step. The fixing ability composition of the present invention may be supplied as a liquid or a powder. When supplied as a liquid, it may be a working liquid or a concentrated liquid.

The processing liquids preferably used in the processing of color light-sensitive materials will be described below. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process),
It 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.

Examples of the bleaching agent contained as a main component of the bleaching solution and the bleach-fixing solution of the present invention include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate and bromate. Partially organic compounds of ferric aminopolycarboxylic acid complex and ferric aminopolyphosphonate can be mentioned.
In the present invention, it is preferable to use a ferric aminopolycarboxylic acid complex salt in view of environmental protection, handling safety, metal corrosiveness and the like.

The following are specific examples of the ferric aminopolycarboxylic acid complex salt in the present invention, but the present invention is not limited thereto. In addition, the oxidation-reduction potential is described. No. Compound Redox potential (mV vs. NHE, pH = 6) 1. N- (2-acetamido) iminodiacetic acid ferric complex 180 2. Methyl iminodiacetic acid ferric complex 200 3. Iminodiacetic acid second Iron complex salt 210 4. Ferric salt of 1,4-butylenediamine tetraacetic acid 230 230 5. Ferric complex of diethylene thioether diamine tetraacetic acid 230 6. Ferric complex salt of glycol ether diamine tetraacetic acid 240 7. 1,3-propylene diamine Ferric tetraacetate complex 250 8. Ferric ethylenediaminetetraacetate complex 110 9. Ferric diethylenetriaminepentaacetate complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic ferric acid salt 80

The oxidation-reduction potential of the bleaching agent is determined by the method described in Transactions of the Faraday Society, vol. 55 (1959), pp. 1312-1313. It is defined by the oxidation-reduction potential obtained by measurement. In the present invention, a bleaching agent having an oxidation-reduction potential of 150 mV or more is preferable from the viewpoint of rapid processing and a viewpoint of effectively exerting the effects of the invention, more preferably a bleaching agent having an oxidation-reduction potential of 180 mV, most preferably 200 mV or more. is there. If the oxidation-reduction potential is too high, bleaching fog occurs, so the upper limit is 700 mV or less, preferably 500 mV.
mV or less. Among them, particularly preferred is a ferric complex of 1,3-propylenediaminetetraacetic acid of compound No. 7.

The aminopolycarboxylic acid ferric complex salt is used as a salt of sodium, potassium, ammonium or the like.
Ammonium salts are preferred because of the fastest bleaching. The amount of the bleaching agent used in the bleaching solution is preferably 0.17 to 0.7 mol per liter of the bleaching solution. preferable.
Particularly preferred is 0.30 to 0.6 mole. The amount of the bleaching agent used in the bleach-fixing solution is 0.01 to 0.5 mol per liter of the bleach-fixing solution, preferably 0.02 to 0.5 mol.
0.2 mol. In the present invention, the bleaching agents may be used alone or in combination of two or more. When two or more bleaching agents are used in combination, the total concentration may be within the above-mentioned range.

When the ferric aminopolycarboxylic acid complex salt is used in the bleaching solution or the bleach-fixing solution, it can be added in the form of a complex salt as described above. A complex salt may be formed in the treatment solution in the presence of a ferric salt (for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate). In the case of this complex formation, the aminopolycarboxylic acid may be added slightly in excess of the amount required for complex formation with ferric ions, and usually 0.01 to 10% when added in excess. It is preferable to make the range excessive.

The bleaching solution as described above generally has a pH of 2
Used in 7.0. In order to speed up the processing, the pH of the bleaching solution is preferably from 2.5 to 5.0, more preferably from 3.0 to 4.8, and particularly preferably from 3.5 to 4.5.
It is preferable that the replenisher is usually used in the range of 2.0 to 4.2. In the present invention, a known acid can be used to adjust the pH to the above range. As such an acid, an acid having a pKa of 2 to 5.5 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and is a value determined at an ionic strength of 0.1 mol / dm and 25 ° C. It is preferable that the bleaching solution contains 0.5 mol / liter or more of an acid having a pKa in the range of 2.0 to 5.5, since bleaching fog and precipitation of the replenisher due to aging at low temperatures can be prevented. This pKa is 2.0 to 5.5.
Examples of the acid include inorganic acids such as phosphoric acid, acetic acid, malonic acid,
Although any organic acid such as citric acid may be used, an organic acid having a carboxyl group is particularly preferable. pKa is 2.
The organic acid of 0 to 5.5 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, it can be used as a metal salt (for example, a sodium or potassium salt) or an ammonium salt if its pKa is in the range of 2.0 to 5.5 described above.
Further, two or more organic acids having a pKa of 2.0 to 5.5 can be used in combination.

[0036] pKa2.
Preferred specific examples of the organic acid of 0 to 5.5 include aliphatic acetic acid, monochloroacetic acid, glycolic acid, propionic acid, lactic acid, glycolic acid, acrylic acid, butyric acid, isobutyric acid, pivalic acid, and aminobutyric acid. Monobasic acids; amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine and leucine; benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy; Basic acids; oxalic acid, malonic acid, succinic acid, tartaric acid,
Aliphatic dibasic acids such as malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid and adipic acid; amino acid dibasic acids such as aspartic acid, glutamic acid and cystine; aromatics such as phthalic acid and terephthalic acid Group dibasic acids;
Various organic acids such as polybasic acids such as citric acid can be listed. Among these, dibasic acids having a carboxyl group are preferred, and succinic acid, maleic acid and glutaric acid are particularly preferred. The amount of these organic acids used is bleaching solution 1
0.2 to 2 mol per liter, preferably 0.4 to 1.
0 mol. These acids are preferable because the effects of the present invention are more remarkably exhibited and bleaching fog is suppressed without odor. The total amount of these acids used is preferably at least 0.3 mol per liter in the form of a bleaching solution. Preferably it is 0.4-2.0 mol / l. More preferably, it is 0.5 to 1.0 mol / liter.

When adjusting the pH of the bleaching solution to the above range, the acid and the alkali agent (for example, ammonia water, KOH,
NaOH, imidazole, monoethanolamine, diethanolamine) may be used in combination. Among them, aqueous ammonia is preferable.

As the alkaline agent used for the bleaching starter when adjusting the starting solution of the bleaching solution from the replenisher,
It is preferable to use potassium carbonate, aqueous ammonia, imidazole, monoethanolamine or diethanolamine. Further, the replenisher may be used as it is without using a bleaching starter.

Various bleaching accelerators can be added to the bleaching solution, the bleach-fixing solution or the prebath thereof used in the present invention. Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858, German Patent 1,290,821, British Patent 1,138,
No. 842, JP-A-53-95630, and compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978), and JP-A-50-140129. Thiazolidine derivatives described in US Pat. No. 3,706,561
Thiourea derivative described in JP-A-58-162
No. 35, iodide, German Patent 2,748,
For example, polyethylene oxides described in JP-A-430-430, and polyamine compounds described in JP-B-45-8836 can be used. Particularly preferred are mercapto compounds as described in British Patent No. 1,138,842 and Japanese Patent Application No. 1-11256.

In the bleaching solution and the bleach-fixing solution used in the present invention, in addition to the bleaching agent and the above compounds, bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride , Ammonium chloride and the like.
The concentration of the rehalogenating agent is 0.1 to 5.0 mol, preferably 0.5 to 3.0 mol per liter in a state of a processing solution.
Is a mole. Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

In the present invention, it is preferable to employ a replenishment method, and the replenishment amount of the bleaching solution or the bleach-fixing solution is preferably 600 ml or less, more preferably 100 to 500 ml, per m ² of the photographic material. Further, the bleaching or bleach-fixing processing time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less. In the treatment, it is preferable that the bleaching solution using the aminopolycarboxylic acid ferric complex salt is subjected to aeration to oxidize the resulting aminopolycarboxylic acid iron (II) complex salt. This causes the drift
The whitening agent ( oxidizing agent ) is regenerated and the photographic performance is kept very stable. The processing liquid used for each processing in the present invention,
It is preferable to perform so-called evaporation correction, which supplies water corresponding to the amount of evaporation. There is no particular limitation on the specific method for replenishing such water.
A monitor water tank separate from the bleaching tank described in JP-A Nos. 4959 and 1-254960 was installed, the amount of water evaporation in the monitor tank was determined, and the amount of water evaporation in the bleaching tank was calculated from the amount of water evaporation. However, a method of replenishing the bleaching tank with water in proportion to the amount of evaporation is disclosed in Japanese Patent Application Nos. 2-46743 and 2-4777.
No. 7, No. 2-47778, No. 2-47779, No. 2
An evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A-117972 is preferable.

In the solution having fixing ability, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg, sodium acetaldehyde bisulfite) are used as preservatives. ) Can be contained. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.

Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the solution having fixing ability 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 addition amount of the chelating agent is 0.01 to 0.3 mol, preferably 0.03 to 0.2 mol, per liter of the treatment liquid.

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 7 to 8. Further, in the bleach-fixing solution, 6 to 8.5 is preferable, and 6.5 to 8.0 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 preferred to contain compounds in the range of 9.0. As these compounds, imidazoles such as imidazole and 2-methyl-imidazole are preferred. These compounds are preferably used in an amount of 0.1 to 1 per liter of the processing solution.
0 mol, preferably 0.2 mol to 3 mol.

When the replenishment method is adopted, the replenishment amount of the solution having the fixing ability is usually 2,000 per m ² of the light-sensitive material.
ml or less, preferably 100-2000 ml,
More preferably, 200 to 800 ml, particularly preferably,
300-600 ml. Here, the replenishing amount is the amount of the replenishing solution containing the fixing agent, and when the overflow solution such as the subsequent washing water is introduced into the bath having the fixing ability, the amount of the replenishing solution is also added. The effect of the present invention becomes remarkable as the replenishment amount becomes lower. In addition to the replenishment of the fixer replenisher, it is preferable to add a post-bath washing water or a stabilizing solution to the fixing solution. In this case, part or all of the overflow solution of the processing solution in the post-bath may be introduced into a bath having a fixing ability, or the processing solution in the processing bath may be directly sent to a bath having a fixing ability by a pump. May be.

In the present invention, the total processing time of the processing with the liquid having a fixing ability is 0.5 to 4 minutes, preferably 0.5 to 2 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 45 seconds to 4 minutes,
More preferably, it is 1 minute to 2 minutes. The processing temperature is 25 to 50 ° C, preferably 35 to 45 ° C.

The solution having fixing ability of the present invention can be recovered by a known method, and a regenerating solution having such recovered silver can be used. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (Japanese Patent Application Laid-Open No. 52-73037, and German Patent No. 2,33).
No. 1,220), ion exchange method (JP-A-51-17)
No. 114, 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 processing step using a liquid having a fixing ability, a washing step is usually performed. It is also possible to use a simple processing method in which a stabilization treatment using a stabilizing solution is performed without performing substantial washing with water after processing with a liquid having a fixing ability. The washing water used in the washing step can contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant However, it is preferable to use a nonionic surfactant, 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 may contain various antibacterial agents and fungicides for preventing generation of water rust and molds generated in the processed photosensitive material. Examples of these antibacterial and antifungal agents are disclosed in
Thiazolyl benzimidazole compounds as shown in JP-A-157244 and 58-105145, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds as typified by trichlorophenol , Bromophenol compounds, organotin and organozinc compounds, acid amide compounds, diazines and triazine compounds, thiourea compounds, benzotriazole compounds, alkylguanidine compounds, quaternary such as benzalkonium chloride Ammonium salts, antibiotics typified by penicillin, etc., are available from Journal Antibact. Antifung.
Agents) Vol 1. No.5, p. 207-223 (198
These include the general-purpose anti-blur agents described in 3).
More than one species may be used in combination. Also, JP-A-48-83820
Various disinfectants described in the above item can also be used. Among them, isothiazolone compounds, in particular, 1,2-benzisothiazolin-3-one are preferable. The addition amount of this compound is 10 to 5 per liter of washing water or a stable liquid.
00 mg.

It is preferable that the washing water contains various chelating agents. Preferred chelating agents include
Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid,
Examples thereof include organic phosphonic acids such as diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345172A1. Further, it is preferable that a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution is contained in the washing water.

The washing step and the stabilizing step are preferably performed in a multi-stage countercurrent system, and the number of stages is preferably two to four. The replenishment amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area. Tap water can be used as the water used in these washing steps, but Ca, M, etc. may be used depending on the ion exchange resin or the like.
It is preferable to use water deionized to a g ion concentration of 5 mg / liter or less, water sterilized by halogen, an ultraviolet germicidal lamp, or the like. In addition, tap water may be used as water for correcting the amount of 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.

Each replenisher of the present invention is used for replenishing the processing solution with a compound which decreases due to deterioration of the photosensitive material during processing or deterioration with time in an automatic processor, and conversely, the concentration of the compound eluted from the photosensitive material by processing. Is adjusted to keep the performance constant. Therefore, the decreasing compound is at a higher concentration than the treatment solution, and the latter compound is at a lower concentration. Compounds that hardly change in concentration due to treatment or aging are usually contained at approximately the same concentration as the treatment solution.

The stabilizing solution can contain all the compounds that can be added to the above-mentioned washing water. In particular, various surfactants for preventing unevenness of water droplets during drying of the processed photosensitive material, various antibacterial agents for preventing generation of water residue and mold generated on the processed photosensitive material, and fungicide. Germicides, fungicides and chelating agents. Further, a pyrazole or a pyrazole derivative having no N-methylol group may be added. Further, in addition to the compound of the present invention, a compound which stabilizes a dye image, for example, hexamethylenetetramine, a hexamethylenetetramine derivative, hexahydrotriazine, a hexahydrotriazine derivative, dimethylolurea, an organic acid or a pH buffer is contained. Is also good. Also,
In addition, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, a fluorescent brightener, a hardener, or an alkanolamine described in US Pat. No. 4,786,583 can be used. The pH of the stabilizer used in the final treatment step is usually in the range of 4 to 9, but is preferably 6 to 8. When the stabilizer of the present invention is used in the final processing step, the replenishing amount is preferably from 200 to 1500 ml, more preferably from 300 to 600 ml, per m ^{2 of the} light-sensitive material to be processed. When using the stabilizer of the present invention in the final treatment step, the treatment temperature is preferably 30 to 45 ° C. The processing time is preferably from 10 seconds to 2 minutes, particularly preferably from 15 to 30 seconds.

Normally, a silver halide color photographic light-sensitive material is subjected to imagewise exposure, and then a negative type and a direct positive type photographic material are subjected to color development. After that, color development is performed. The color developing solution that can be used in the present invention is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Preferred color developing agents are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-1 N, N-diethyl-p-phenylenediamine D-2 2-Methyl-N, N-diethyl-p-phenylenediamine D-3 4- [N-ethyl-N- (β-hydroxyethyl) amino] Aniline D-4 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-Amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline D-7 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-8 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline Among the above-mentioned p-phenylenediamine derivatives, particularly preferred are D-4 and D-6. Further, these p-phenylenediamine derivatives are sulfates, hydrochlorides, sulfites,
It may be a salt such as p-toluenesulfonic acid salt. The amount of the aromatic primary amine color developing agent used is preferably from 0.001 to 0.1 mol, more preferably from 0.01 to 0.06 mol, per liter of the color developing solution.

If necessary, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be used as a preservative in the color developing solution. Can be added. The preferable addition amount of these preservatives is 0.5 to 10 per liter of the color developing solution.
g, more preferably 1 to 5 g.

Further, as a compound for directly preserving the aromatic primary amine color developing agent, JP-A-63-53163
Various hydroxylamines (compounds having a sulfo group or a carboxy group are preferred) described in JP-A Nos. 41 and 63-106655, hydroxamic acids described in JP-A-63-43138, and JP-A-63-146041. Hydrazines and hydrazides; phenols described in JP-A-63-44657 and JP-A-63-58443;
Α-hydroxyketones and α-
Examples thereof include aminoketones and various sugars described in JP-A-63-36244. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in 3-27841 and 63-25654, 63-30845 and 63-146.
No. 40, diamines described in 63-43139 and the like,
Nos. 63-21647, 63-26655 and 6
Polyamines described in 3-44655, 63-53;
The nitroxy radicals described in No. 551, 63-43;
Alcohols described in No. 140 and 63-53549, oximes described in 63-56654 and 6
Tertiary amines described in JP-A-3-239647 can be used. Other preservatives include JP-A-57-441.
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, 54
Alkanolamines described in -3582, 56-
If necessary, polyethyleneimines described in U.S. Pat. No. 94349 and aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 may be contained. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0. In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-2
Potassium-hydroxybenzoate (potassium 5-sulfosalicylate); The amount of the buffer added is preferably 0.1 mol or more per liter of the color developing solution, and particularly preferably 0.1 to 0.4 mol.

In addition, it is preferable to use various chelating agents in the color developing solution as an agent for preventing precipitation of calcium and magnesium or for improving the stability of the color developing solution. Organic acid compounds are preferred as the chelating agent,
Examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Representative examples of these are diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid and the like. These chelating agents may be used in combination of two or more as necessary. The chelating agent may be added in an amount sufficient to block metal ions in the color developing solution, for example, about 0.1 g to 10 g per liter of the color developing solution.

An optional development accelerator can be added to the color developer if necessary. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means that the color developer contains no more than 2 ml, preferably no color developer per liter. Other development accelerators include JP-B-37-16
No. 088, No. 37-5987, No. 38-7826,
Thioether compounds described in JP-A Nos. 44-12380 and 45-9019, U.S. Pat. No. 3,818,247, JP-A-52-49829 and JP-A-50-15554.
P-phenylenediamine compound described in JP-A No.
Quaternary ammonium salts described in JP-A-0-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; U.S. Pat.
No. 03, No. 3,128,182, No. 4,230,
No. 796, No. 3,253,919, Japanese Patent Publication No. 41-1
No. 1431; U.S. Pat. Nos. 2,482,546; 2,596,926; 3,582,346; and JP-B-37-16088 and 42-25201. U.S. Pat. No. 3,128,183.
No., JP-B No. 41-11431, 42-23883
And polyalkylene oxides described in U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3-pyrazolidones, imidazoles and the like can be added as necessary. The addition amount of the development accelerator is about 0.01 g to 5 g per liter of the color developing solution.

In the present invention, if necessary,
Optional antifoggants can be added. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. The amount of the antifoggant added is about 0.001 g to 1 g per liter of the color developing solution. The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4′-diamino-2,2′-disulfostilbene compound is preferable. The amount of the fluorescent whitening agent is from 0 to 5 g, preferably from 0.1 g to 4 g, per liter of the color developing solution. Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The color developing replenisher contains compounds contained in the color developing solution. The role of the color developing replenisher is to control the concentration of the compound eluted from the light-sensitive material by the processing of the light-sensitive material and the replenishment of the compound to the color developing solution, which is reduced by deterioration over time in an automatic processor, and vice versa. In this case, the developing performance is kept constant. Therefore, the former compound has a higher concentration than the color developing tank solution,
Also, the latter compound has a low concentration. The former compound is a color developing agent or a preservative, and the replenisher contains 1.1 to 2 times the amount of the tank solution. The latter compound is a development inhibitor typified by a halide (for example, potassium bromide).
0.6 times. The concentration of the halide in the replenisher is usually 0.006 mol / l or less, but the lower the replenishment, the lower the concentration needs to be. Compounds that hardly change in concentration due to processing or aging are usually contained at approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the replenisher for color development is 0.05 to 0.
Increase by about 5 This difference in pH also needs to increase with decreasing replenishment. The replenishment amount of the color developing solution is 3000 ml or less per 1 m ² of the light-sensitive material.
Preferably it is 1500 ml.

The processing temperature of the color developing solution is suitably from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is suitably from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 20 seconds, and more preferably from 1 minute to 2 minutes and 30 seconds. Further, the color developing bath may be divided into two or more baths as necessary, and a color developing replenisher may be replenished from the first or last bath to shorten the developing time and further reduce the replenishing amount.

The processing method of the present invention can be preferably used for color reversal processing. In the reversal process, after the black and white development, the reversal process is performed as necessary, and then the color development is performed. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used in a reversal process of a color photosensitive material, and is a black-and-white developing solution used in a processing solution of a black-and-white silver halide photosensitive material. Various well-known additives used in addition to the liquid can be contained.

Typical additives include 1-phenyl-
Developing agents such as 3-pyrazolidone, methol and hydroquinone; preservatives such as sulfites; accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; potassium bromide and 2-methylbenzimidazole; Examples thereof include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphate, and development inhibitors comprising a small amount of iodide or a mercapto compound.

When processing is carried out by an automatic developing machine using the above black-and-white developer or color developing solution, the area (opening area) of the developing solution (color developing solution and black-and-white developing solution) in contact with air should be as small as possible. preferable. For example, opening area (cm ² )
Is divided by the volume of the developing solution (cm ³ ), and the opening ratio is preferably 0.01 (cm ⁻¹ ) or less.
005 or less is more preferable.

The developer can be regenerated and used.
Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more. As processing using developer regeneration, after regenerating the overflow solution of the developer,
Use as replenisher. As a regeneration method, it is preferable to use an anion exchange resin. Regarding the particularly preferred composition of the anion exchange resin and the method of regenerating the resin, see DIAION MANUAL (I) (198) issued by Mitsubishi Chemical Industry Co., Ltd.
6th, 14th edition). Among the anion exchange resins, resins having the composition described in JP-A-2-952 and JP-A-1-281152 are preferable.

Adjusting baths used for the inversion treatment include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Aminopolycarboxylic acid chelating agents such as 3-diaminopropanetetraacetic acid and cyclohexanediaminetetraacetic acid; sulfites such as sodium sulfite and ammonium sulfite; and various types of bleaching solutions such as thioglycerin, aminoethanethiol and sulfoethanethiol A bleaching accelerator can be included. For the purpose of preventing scum, sorbitan esters of ethylene oxide-substituted fatty acids described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure, Vol. It is preferable to contain the described polyoxyethylene compound or the like. These compounds can be used in a range of 0.1 g to 20 g per liter of the adjustment liquid, but preferably in a range of 1 g to 5 g. The conditioning bath preferably contains an image stabilizer which can be used in the above-mentioned stabilizing solution to have a stabilizing effect. The pH of the adjusting bath is usually used in the range of 3 to 11, preferably 4 to 9,
More preferably, it is 4.5-7. The processing time in the conditioning bath is preferably 30 seconds to 5 minutes. The replenishing amount of the adjusting bath is 30 ml to 3000 ml per 1 m ² of the photosensitive material.
However, it is particularly preferably 50 ml to 1500 ml. The treatment temperature of the conditioning bath is preferably from 20C to 50C, and particularly preferably from 30C to 40C.

It is preferable to use a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath, because the amount of waste liquid can be reduced. In processing, not only bleaching solution, bleach-fixing solution and fixing solution, but also other processing solutions (for example, color developing solution, washing water, and stabilizing solution), use an appropriate amount of water or correction solution to correct concentration due to evaporation. It is preferable to replenish the solution or the processing replenisher.

In the present invention, the effect is particularly effective when the total processing time of the processing solution from the bleaching process to the drying step is from 1 minute to 3 minutes, preferably from 1 minute to 20 seconds to 2 minutes. .

In the present invention, the drying temperature is from 50 to 65.
C is preferable, and 50 to 60 C is more preferable. The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. The number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited. As a typical example, on a support,
A silver halide color photographic light-sensitive material having a light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities, wherein the light-sensitive layers are blue light, green light and red light. A unit photosensitive layer having color sensitivity to any of light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally such that a red-sensitive layer, a green color-sensitive layer Layer and a blue-sensitive layer in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748,
Nos. 9-113438, 59-113440, 61
Couplers such as those described in JP-A-20037 and JP-A-61-20038, and may contain a color-mixing inhibitor, an ultraviolet absorber, an anti-stain agent and the like as usually used. .

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of layers can be preferably used. 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. Also, JP-A-57-112751, JP-A-62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.
As a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) /
Alternatively, they can be installed in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-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 and JP-A-62-63.
As described in JP-A-936-936, an order of blue-sensitive layer / GL / RL / GH / RH can be arranged from the side farthest from the support. In addition, Japanese Patent Publication No. 49-15495
The upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower sensitive silver halide emulsion layer, and the lower layer is less sensitive than the middle layer as described in An example is an arrangement in which a silver emulsion layer is disposed, and the sensitivity is sequentially lowered toward the support, and the sensitivity is sequentially reduced to three layers having different sensitivities. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The dry film thickness of all the constituent layers except the support and the undercoat layer and the back layer of the support is preferably from 12.0 to 20.0 μm from the viewpoint of bleaching fog and stain with time. More preferably, it is 12.0 to 17.0 µ.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
The photosensitive material was stored under conditions of 5 ° C. and 50% RH for 7 days after the preparation, first, the total thickness of the photosensitive material was measured, and then, after removing the coating layer on the support, 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 thickness is measured, for example, by a film thickness measuring device (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. Further, a photograph of a cross section of the above-mentioned photosensitive material can be taken using a scanning electron microscope (preferably at a magnification of 3,000 or more), and the total thickness on the support can be measured.

The swelling ratio of the photosensitive material in the present invention [(25
Equilibrium swollen film thickness in H ₂ O at 25 ° C., dry film thickness at 55% RH / dry film thickness at 25 ° C., 55% RH) ×
100] is preferably 50 to 200%, and 70 to 150%
Is more preferred. If the swelling ratio deviates from the above value, the residual amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the film swelling speed of the light-sensitive material in the present invention is defined as a saturated swelling film thickness which is 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds). When the time required to reach this 1/2 film thickness is defined as the swelling speed T1 / 2, T1 / 2 is preferably 15 seconds or less. More preferably, it is 9 seconds or less.

The silver halide contained in the photographic emulsion layer of the light-sensitive material used in the present invention may be any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver bromide and silver chloride. Good.
Preferred silver halides are silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 0.1 to 30 mol% of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% iodide.

The silver halide grains of the photographic emulsion are cubic,
Those having regular crystals such as octahedron and tetrahedron,
Those having an irregular crystal form such as a sphere or a plate, those having a crystal defect such as a twin plane, or a composite form thereof may be used.

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, for example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, "I. Emulsion preparation and types" and No. 187
16 (November 1979), p. 648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glaf)
kides, Chimie et Physique Photographique Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Daffin, published by Focal Press (GF Duffin, Photographic E).
mulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikuman et al., published by Focal Press (VLZelikman et al Makingand Coating).
Photographic Emulsion, Focal Press, 1964). U.S. Pat. Nos. 3,574,628 and 3,655,39
No. 4 and British Patent No. 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science, Inc.
And Engineering (Gutoff, Photographic Sci
14, 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, and 4,430,048;
No. 4,439,520 and British Patent No. 2,112,
No. 157 or the like.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a phase structure. Further, silver halides having different compositions may be joined by an epitaxial junction,
Further, 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.

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 No. 17643 (December 1978) and No. 1
8716 (November 1979) and No. 30710
5 (November 1989), and the corresponding portions are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures (RD), 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, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right Columns 866 to 868 Super sensitizer 〜Page 649 Right column 4. Brightener 24 Page 647 Page 868 Right column Page 868 5.Fogging prevention Page 24 to 25 Page 649 Right column 868 to 870 Agents, stabilizers 6. Light absorbers, page 25-26, page 649, right column, page 873 Filters-page 650, left column, dyes, ultraviolet absorbers 7.Stain, page 25, right column, page 650, left column, page 872 Inhibitors-right column 8. Dye image, page 25 Page 650, left column, page 872 Stabilizer 9. Hardener page 26, page 651, left column, pages 874 to 875 10. Binder, page 26, page 651, left column, 873 to 874 11. Plasticizer, page 27, page 650, right column, page 876 Lubrication Agent 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static page 27, page 650, right column, pages 876 to 877 Inhibitor 14. Matting agent, pages 878 to 879

In the present invention, various color couplers can be used in combination. A typical specific example is RD No. 1
7643, VII-CG and RD No. 307105, VII-CG
The patent is described in US Pat.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620;
Nos. 4,326,024 and 4,401,752
No. 4,248,961, JP-B-58-1073
9, UK Patent Nos. 1,425,020 and 1,47
No. 6,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and EP 249,473A are preferred.

As the magenta coupler, 2-equivalent and / or 4-equivalent 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat.
No. 4,351,897, European Patent 73,636
No. 3,061,432 and US Pat. No. 3,72.
No. 5,064, RD No. 24220 (June 1984
), JP-A-60-33552, RD No. 24230
(June 1984), JP-A-60-43659, 6
No. 1-72238, No. 60-35730, No. 55-1
Nos. 18034, 60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, WO (PCT) 88/047.
No. 95 is more preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 052,212, No. 4,146,396, No. 4,228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826
No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat. Nos. 3,446,622 and 4,333,99.
No. 9, 4,753, 871, 4,451, 5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4,254,212, No. 4,29
No. 6,199, and JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in RD No. 17643, Sections VII-G,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,1
38,258, British Patent No. 1,146,368 and Japanese Patent Application No. 2-50137 are preferred. Also,
A coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a dye reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming as a leaving group. U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Publication) No. 3,234 are examples of couplers in which a coloring dye has an appropriate diffusibility. , 533 are preferred.

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
Nos. 09,320, 4,576,910 and British Patent 2,102,173. Couplers which release a photographically useful residue upon coupling can also be preferably used. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157538 and JP-A-59-170840. Those described in the above item are preferred. Other couplers that can be used in the light-sensitive material of the present invention include US Pat.
Competitive couplers described in US Pat.
Nos. 73,302A, RD Nos. 11449 and 24241, which release dyes which recolor after release.
Bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, and couplers releasing leuco dyes described in JP-A-63-75747. U.S. Pat.
74,181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027 and the like. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, etc.) Tridodecyl phosphate, tributoxyethyl phosphate,
Trichloropropylphosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide) , N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
Ert octylaniline and the like; hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used.
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of latexes for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
No. 2,541,230 and the like.
These couplers can be impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the high boiling point organic solvent,
Alternatively, it can be dissolved in a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

Next, the case where the present invention is used for processing a silver halide black-and-white photosensitive material will be described. The developer used in developing the silver halide black-and-white photosensitive material can contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, and a chelating agent). For the treatment of the present invention, any of the known methods can be used, and a known treatment solution can be used. or,
The processing temperature is usually chosen between 18 ° C and 50 ° C,
The temperature may be lower than 18 ° C or higher than 50 ° C. Black-and-white developers include dihydroxybenzenes, 1-
Known developing agents such as phenyl-3-pyrazolidones and aminophenols can be used alone or in combination. Examples of the dihydroxybenzene-based developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone. Of these, hydroquinone is particularly preferred. Examples of 1-phenyl-3-pyrazolidone or a derivative thereof as an auxiliary developing agent include 1-phenyl-3-pyrazolidone.
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol auxiliary developing agents include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p
-Aminophenol is preferred. The dihydroxybenzene-based developing agent is usually preferably used in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / L to 0.5 mol / L, and the latter is 0.06 mol / L. It is preferably used in an amount of not more than 1 / liter. As the sulfite preservative used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
There are sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like.

Sulfite is used in an amount of 0.3 mol / l or more in a black-and-white developer, particularly a developer for graphic arts. Preferably it is mol / l. Sodium hydroxide, potassium hydroxide, sodium carbonate, the alkaline agent used in the developer of the present invention,
It contains pH adjusters and buffers such as potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate and potassium silicate. Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve Organic solvents such as hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, sodium 2-mercaptobenzimidazole-5-sulfonate, indazole compounds such as 5-nitroindazole, A fog inhibitor such as a benztriazole-based compound such as 5-methylbenztriazole or a black pepper inhibitor; and, if necessary, a color tone agent, a surfactant,
It may contain an antifoaming agent, a water softener, a hardening agent, and the like.

The developer used in the present invention may contain a compound described in JP-A-56-24347 as a silver stain inhibitor.
Compounds described in JP-A-62-212651 as an uneven development inhibitor, and Japanese Patent Application No. 60-109743 as a dissolution aid.
Can be used. In the developer used in the present invention, a buffering agent is disclosed in Japanese Patent Application No. 61-2870.
8, saccharides (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate (for example, sodium) described in JP-A-60-93433. Salt, potassium salt) and the like.

The fixing solution is an aqueous solution containing a hardening agent (for example, a water-soluble aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid, citric acid or a salt thereof), if necessary, in addition to the fixing agent. , PH 3.8 or more, more preferably 4.0 to 7.5. The water-soluble aluminum salt that mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. Tartaric acid (containing Na,
K salt) or a derivative thereof, citric acid (including Na,
K salt, etc.) or derivatives thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective.

The fixing solution may further contain a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, ammonia or sulfuric acid), an image preserving agent (for example, potassium iodide), if desired.
A chelating agent can be included. Here, the pH buffer is
Since the pH of the developer is high, it is used in an amount of 10 to 40 g / l, more preferably about 18 to 25 g / l. The fixing temperature and time are the same as in the case of development, and
It is preferably 10 seconds to 1 minute at 0 ° C. Other than the above, the description is based on the description of the fixing solution used in the processing of the color photographic material. Further, the washing water may contain a fungicide (for example, a compound described in Horiguchi's "Bacterial Prevention and Prevention Chemistry", Japanese Patent Application No. 60-253807), a washing accelerator (such as a sulfite), a chelating agent and the like. May be contained. The replenishment amount of washing water is 120
It may be 0 ml / m ² or less (including 0). The case where the replenishment amount of the washing water (or the stabilizing solution) is 0 means a washing method by a so-called pooled water washing method. As a method for reducing the amount of replenishment, a multi-stage countercurrent method (for example, two-stage, three-stage, etc.) has been known for a long time.

For the problem that occurs when the replenishing amount of water such as washing water is small, good processing performance can be obtained by combining the techniques described in the above-described processing of the color photographic material.

In the method of the present invention, when washing with a small amount of water, the method is described in JP-A-63-18350 and JP-A-62-28.
It is more preferable to provide a squeeze roller and a crossover rack cleaning tank described in No. 7,252 or the like. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the water subjected to the antifungal means to the washing or stabilizing bath according to the present invention is disclosed in
As described in JP-A-235-133 and JP-A-63-129343, the present invention can also be used for a processing solution having a fixing ability, which is the preceding processing step. Further, a water-soluble surfactant and / or an antifoaming agent are used to prevent unevenness of water bubbles easily generated when washing with a small amount of washing water and / or to prevent a treatment agent component attached to a squeeze roller from being transferred to a treated film. It may be added. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing tank to prevent contamination by dyes eluted from the photosensitive material.

According to the above method, the developed and fixed photographic material is washed with water and dried. The water washing is performed in order to almost completely remove the silver salt dissolved by the fixing.
Preferred is about 50 ° C. for 10 seconds to 3 minutes. Drying is about 40 ° C ~
The drying is performed at about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but usually about 5 seconds to 3 minutes 30 seconds.
U.S. Patent No. 30 discloses a roller transport type automatic developing machine.
No. 25779, No. 3,545,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method. The fixing solution of the present invention and the developing solution used in the present invention are disclosed in
It is preferable to store in a packaging material having low oxygen permeability described in -73147. The processing solution used in the present invention is preferably a replenishing system described in JP-A-62-91939.

Examples of the photographic light-sensitive material according to the present invention include ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive materials for photography, X-ray black-and-white light-sensitive materials, black-and-white light-sensitive materials for printing), and ordinary multilayer halogenated light-sensitive materials. Silver color photographic light-sensitive materials (eg, color negative film, color reversal film, color positive film, color negative film for movies, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light-sensitive material for laser scanners And the like.

The thickness of the support of the color negative film used in the present invention is preferably from 70 to 130 μm. The material of the support is described in JP-A-4-124636, page 5, upper right column, line 1, line 6 to page 6, upper right. Various plastic films described in column 5, line 5 can be used, and 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). It is preferable to use polyester for the support of the film used in the present invention since a higher draining effect can be obtained.

The support of the color negative film used in the present invention includes a support having a conductive layer and a transparent magnetic material layer on one surface as described in JP-A-4-62543.
International Patent Publication WO90 / 04205, FIG. 1
A having a magnetic recording layer described in A.
No. 124628, which has a stripe magnetic recording layer,
In addition, those having a transparent magnetic recording layer adjacent to the stripe magnetic recording layer are also preferable. It is preferable to provide a protective layer described in JP-A-4-73737 on these magnetic recording layers. The package (patrone) for accommodating the color negative film of the present invention may be of any type currently used or known, and in particular, US Pat. No. 4,834,30.
No. 6, FIG. 1 to FIG. 3 or
U.S. Pat. No. 4,846,418, FIG. 1-FI
G. FIG. Those described in No. 3 are preferred.

[0105]

According to the present invention, a novel fixing composition comprising the compound of the formula (I) alone or in combination with a fixing agent such as thiosulfate can be provided. That is, the compound represented by the general formula (I) can be used as a fixing agent or a fixing accelerator. According to the present invention, a processing method in which fixing is not delayed even when the replenishment amount is reduced can be performed. For example, as the photosensitive material 1 m ² per 200～800Ml, even lower the replenishing amount, it is possible to desilvering without fixing is delayed.

[0106]

The present invention will be described in more detail with reference to the following examples. Example 1 On a subbed cellulose triacetate film support,
Samples 101, which are multilayer color photosensitive materials, were prepared by applying each layer having the composition shown below in multiple layers. (Composition of photosensitive layer) Materials used for each layer are classified as follows: ExC: Cyan coupler HBS: High boiling point organic solvent ExM: Magenta coupler ExO: Color mixture inhibitor ExY: Yellow coupler W: Surfactant ExS: sensitizing dye H: gelatin hardener EXU: UV absorber B: polymer S: formalin scavenger or fog inhibitor F: additives (stabilizers, fog inhibiting agents, etc.) number corresponding to each component, g / m ² units The amount of silver halide is shown in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.090 Dispersion A of Organic Solid Disperse Dye 10.0 Dispersion B of Organic Solid Disperse Dye 5.0 Gelatin 1.4

[0108]

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-3 1.5 × 10 ^-4 ExS-4 1.8 × 10 ^-5 ExS-5 2.5 × 10 ^-4 ExC-2 0.020 ExC-3 0.17 ExC-4 0.17 ExC-5 0.020 ExM-3 0.020 ExU-1 0.070 ExU-2 0.050 ExU-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion B Silver 1.60 ExS-3 1.0 × 10 ^-4 ExS-4 1.4 × 10 ^-5 ExS-5 2.0 × 10 ^-4 ExC-1 0.010 ExC-2 0.010 ExC-3 0.050 ExC-4 0.050 ExC-6 0.080 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion G Silver 1.0 ExS-3 1.0 × 10 ^-4 ExS-4 1.4 × 10 ^-5 ExS-5 2.0 × 10 ^-4 ExC-1 0.050 ExC-2 0.015 ExC-3 0.20 ExC-4 0.20 ExC-7 0.20 ExC-8 0.020 ExU-1 0.070 ExU-2 0.050 ExU-3 0.070 HBS-1 0.22 HBS-2 0.10 Gelatin 1.6

Sixth layer (intermediate layer) ExO-1 0.040 ExM-4 0.050 HBS-1 0.020 Gelatin 0.80

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.15 silver iodobromide emulsion B silver 0.15 silver iodobromide emulsion C silver 0.10 ExS-2 5.0 × 10 ^-5 ExS-6 3.0 × 10 ^-5 ExS-7 1.0 × 10 ^-4 ExS-8 3.8 × 10 ^-4 ExM-1 0.021 ExM-3 0.030 ExM-5 0.20 ExM-6 0.0050 ExM-7 0.10 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth layer (intermediate layer) ExM-4 0.018 ExC-8 0.040 HBS-1 0.16 HBS-3 0.0080 Gelatin 0.50

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Silver 1.2 ExS-2 0.50 × 10 ^-5 ExS-6 3.5 × 10 ^-5 ExS-7 8.0 × 10 ^-5 ExS-8 3.0 × 10 ^-4 ExM-3 0.025 ExM-8 0.015 ExM-9 0.50 ExY-1 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.5

Tenth layer (intermediate layer) ExO-1 0.040 HBS-1 0.020 Gelatin 0.80

Eleventh layer (donor layer for multilayer effect on red-sensitive layer) Silver iodobromide emulsion J Silver 1.2 Silver iodobromide emulsion K Silver 2.0 ExS-2 4.0 × 10 ^-4 ExC-2 0.10 ExM-2 0.10 HBS -1 0.10 HBS-2 0.10 Gelatin 0.80

Twelfth layer (yellow filter layer) Yellow colloidal silver silver 0.050 Dispersion B of organic solid disperse dye B 15.0 ExO-1 0.080 HBS-1 0.030 Gelatin 0.95

13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.080 silver iodobromide emulsion B silver 0.070 silver iodobromide emulsion F silver 0.070 ExS-9 3.5 × 10 ^-4 ExC-3 0.042 ExY-2 0.72 ExY-3 0.020 HBS-1 0.28 Gelatin 1.1

Fourteenth Layer (Medium Speed Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Silver 0.45 ExS-9 2.1 × 10 ^-4 ExY-2 0.15 ExC-2 0.0070 HBS-1 0.050 Gelatin 0.78

Fifteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion H 0.77 ExS-9 2.2 × 10 ^-4 ExY-1 0.010 ExY-2 0.60 ExY-3 0.010 HBS-1 0.070 Gelatin 0.69

Sixteenth Layer (Protective Layer) Silver Iodobromide Emulsion I Silver 0.20 ExU-4 0.11 ExU-5 0.17 HBS-1 0.050 Dispersion A of Organic Solid Disperse Dye A 0.50 Dispersion of Organic Solid Disperse Dye B 0.50 W- 1 0.020 H-1 0.40 B-1 (about 1.5 μm in diameter) 0.10 B-2 (about 1.5 μm in diameter) 0.10 B-3 0.020 S-1 0.20 Gelatin 1.8

The samples prepared in this manner include, in addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. W-2,
W-3, B-4 to B-6, F-1 to F-17,
Contains iron, lead, gold, platinum, iridium and rhodium salts.

Preparation of Dispersion A of Organic Solid Disperse Dye ExF-1 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 ml pot mill. , Dye ExF
-1 and 5.0 g of zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion A of a dye.

Preparation of Dispersion B of Organic Solid Disperse Dye ExF-2 shown below was replaced with ExF-1 of Dispersion A described above. The following was prepared similarly to Dispersion A.

[0126]

[Table 1]

In Table 1, (1) Emulsions A to K were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to K were 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-3-237450. Have been. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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The sample prepared as described above was cut into a width of 35 mm, subjected to imagewise exposure, and subjected to running processing by an automatic developing machine. In each running process, a 35 mm wide sample was continuously run for 500 m. The processing steps and the composition of the processing solution are shown below. Processing process Step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 05 seconds 38.0 ° C 400 ml 5 liter Bleaching 50 seconds 38.0 ° C 130 ml 3 liter Fixed (1) 40 seconds 38.0 ° C − 3 liter Fixed (2 ) 40 seconds 38.0 ° C 400 ml 3 liters Rinse 30 seconds 38.0 ° C 440 ml 2 liters Stable (1) 20 seconds 38.0 ° C-2 liters Stable (2) 20 seconds 38.0 ° C 400 ml 2 liters Dry 60 seconds 55 ° C * replenishment rate is countercurrent system, the amount stabilizing and fixing per photosensitive material 1 m ² from (2) to (1).
The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 65 ml / m ^{2 and} 1 m ² per photographic material, respectively.
Milliliters, 50 milliliters, 50 milliliters. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.2 1-hydroxyethylidene-1,1-diphospho 3.3 3.3 Sodium sulfite 3.9 5.2 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 − Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.8 2-Methyl-4- [N-ethyl-N- (β-4.5 7.0 hydroxyethyl) amino] aniline sulfate 1.0 L 1.0 L pH 10.05 10.20

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-diaminopropanetetraacetic acid ferric ammonium 144.0 206.0ium-water salt maleic acid 4060 succinic acid 2030 ammonium bromide 84.0 120.0 ammonium nitrate 17.5 25.0 Hydroxyacetic acid 63.0 Acetic acid 54.2 80.0 Add water 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia) 4.40 4.00

(Fixing solution) Common to tank solution and replenisher Ammonium sulfite 19.0 Aqueous ammonium thiosulfate 280 ml (700 g / L) Additives (Table 2) Imidazole 28.5 Ethylenediaminetetraacetic acid 12.5 Add water 12.5 pH Adjust with ammonia water and acetic acid) 7.40

(Washing water) Common tank water and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IRA) -4
00) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) 1,4-bis (1,2,4-triazol-1-yl 0.6 methyl) piperazine 1,2,4-triazole 1.3 Polyoxyethylene-p-monononylphenyl ether 0.2 (average degree of polymerization 10) Disodium ethylenediaminetetraacetate 0.05 Sodium p-toluenesulfinate 0.05 1,2-Benzoisothiazolin-3-one 0.05 Gentamicin 0.01 1.0 liter with water pH 8.0

After completion of each running process, the unexposed sample 101 was processed, and the amount of residual silver was determined by X-ray fluorescence analysis.
In addition, each fixing after running process (1) 200ml of tank liquid
Each was placed in a polyvin and stored at 10 ° C. and 0 ° C. for 2 weeks, and the presence or absence of a precipitate was examined. Evaluation of the precipitate 0: No precipitation at 10 ° C and 0 ° C storage 1: Slight precipitate formation only at 0 ° C storage 2: Slight precipitate formation at 10 ° C and 0 ° C storage 3: Large precipitation at storage at 0 ° C 4: Large amount of precipitate generated at 10 ° C and 0 ° C storage.
0 ml each, put in 500 ml tall beaker, 40 ℃
And the number of days until the liquid was sulfurized was examined. Table 2 shows the results.

[0151]

[Table 2]

As can be seen from Table 2, the general formula (I) of the present invention
It can be seen that the compound (1) is superior in fixing performance as compared with ammonium thiosulfate, but the effect is remarkably exhibited when used in combination with ammonium thiosulfate. When the compound of the present invention is used in combination with ammonium thiosulfate, if the addition amount is too small, the effect cannot be sufficiently exerted, and if the addition amount is too large, a precipitate is formed in the fixing solution, which is not practical. Therefore, it is understood that the addition amount is preferably 0.05 to 2.0 mol / liter. Further, when the compound of the general formula (I) is used in combination with the compound of the general formula (I), the fixing property and the stability of the fixing solution are improved.

Example 2 A similar effect was obtained for Sample 102 in which the emulsion of Example 1 was replaced with emulsions LP as described below.

[0154]

[Table 3]

[0155]

[Table 4]

Example 3 After the sample 101 produced in Example 1 was exposed, the following processing steps and processing solution were used in an automatic developing machine by the method described below (the cumulative replenishment amount of the fixing (Until three times the volume). (Processing method) Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 13 ml 20 liter Bleaching 3 minutes 00 seconds 38 ° C 25 ml 40 liter Rinse with water (1) 15 seconds 24 ° C From (2) 10 liters to 1) Counterflow piping system Rinse (2) 15 seconds 24 ℃ 15 ml 10 liters Fixed 3 minutes 00 seconds 38 ℃ 15 ml 30 liters Rinse (3) 30 seconds 24 ℃ From (4) to (3) 10 liters Counter flow piping system Rinse (4) 30 seconds 24 ° C 1200 ml 10 liters Stable 30 seconds 38 ° C 20 ml 10 liters Drying 4 minutes 20 seconds 55 ° C * Replenishment amount is 35mm width per 1m length

Next, the composition of the processing solution will be described. (Color developing solution) Same as in Example 1.

(Bleaching solution) Tank solution (g) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric sodium salt 40.0 48.0 3-mercapto-1,2,4-triazole 0.03 0.08 Sodium bromide 140.0 160.0 Sodium nitrate 30.0 35.0 Succinic acid 50.0 60.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water and nitric acid) 4.6 4.0

(Fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.57 Ammonium sulfite 20.0 22.7 Ammonium thiosulfate aqueous solution (700 g / L) 295.0 mL 335.0 mL Additives (Table 5) Acetic acid (90%) 3.3 3.7 1.0 liter with water 1.0 liter pH (adjusted with ammonia water and acetic acid) 6.7 6.8

(Stable liquid) Same as in Example 1.

After completion of each of the running processes, the first embodiment
The amount of residual silver was evaluated in the same manner as described above. (Condition A) A similar test was conducted by replacing ammonium sulfite, ammonium thiosulfate, and aqueous ammonia in the fixing solution with equimolar amounts of sodium sulfite, sodium thiosulfate, and sodium hydroxide, respectively. (Condition B) The results are shown in Table 5.

[0162]

[Table 5]

As is conventionally known, sodium thiosulfate is inferior in fixing performance to ammonium thiosulfate. As can be seen from Table 5, when the compound of the present invention is used in combination with ammonium thiosulfate, not only the fixing performance is improved, but also in combination with sodium thiosulfate, the effect can be remarkably exhibited. In particular, in view of recent environmental problems, removal of ammonia from the treatment waste liquid is desired, but it can be seen that the use of the compound of the present invention can solve that problem.

Example 4 Silver halide grains were precipitated by a double jet method.
After physical ripening and desalting, it is further chemically ripened and silver chloroiodobromide (bromine content: 30 mol%, iodine content: 0.1 mol%)
An emulsion was obtained. The average diameter of silver halide grains contained in this emulsion was 0.3 μm. 0.6 kg of silver halide was contained in 1 kg of this emulsion. This emulsion is
Each kg was weighed, dissolved by heating at 40 ° C., a methanol solution of a sensitizing dye was added, and a predetermined amount of an aqueous solution of sodium bromide was further added. Next, 25 ml of a 1.0% by weight methanol solution of the dye was added, and a 1.0% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added.
0 ml was added, and 40 ml of a 1.0% by weight aqueous solution of dodecylbenzenesulfonic acid sodium salt was further added, followed by stirring. This finished emulsion was coated on a cellulose triacetate film base so as to have a dry film thickness of 5 μm and dried to obtain a sample of a light-sensitive material. These samples were cut and a color temperature of 26
50% blackening exposure was performed using a sensitometer having a light source of 66 ° K. Then, a running process was performed according to the following processing recipe until the cumulative replenishment amount of the fixing solution became three times the capacity of the mother liquor tank.

Processing process Step Processing time Processing temperature Replenishment amount Tank capacity (liter) Current image 20 seconds 38 ° C 320ml 18 Fixation 20 seconds 38 ° C 220ml 18 Rinse 20 seconds 20 ° C 200ml 18 * Replenishment amount: photosensitive material 1m ² Amount per

(Developer) Common to tank solution and replenisher Methol 0.31 g Anhydrous sodium sulfite 39.6 g Hydroquinone 6.0 g Anhydrous sodium carbonate 18.7 g Potassium bromide 0.86 g Citric acid 0.68 g Potassium metabisulfite 1.5 g Add water to 1 liter

(Fixing solution) Common to tank solution and replenisher Sodium thiosulfate 200 g Additive (Table 6) As shown in Table 6 Sodium bisulfite 12.0 g Disodium ethylenediaminetetraacetate 0.1 g Tartaric acid 3.0 g Acetic acid (90%) 20.0 g Sulfuric acid Aluminum (27%) 35.0 g 1 liter with water pH (prepared with sodium hydroxide) 4.1

After the completion of each of the above-mentioned running processes, the amount of silver remaining in the unexposed portions of the processed samples was determined by X-ray fluorescence analysis.
Table 6 shows the results.

[0169]

[Table 6]

Table 6 shows that when the compound of the present invention was used, the fixing ability was remarkably improved.

Example 5 The color photographic paper described in Example 1 of JP-A-5-313281 was processed into a roll having a width of 127 mm, and a printer processor PP1250V manufactured by Fuji Photo Film Co., Ltd. (remodeled so that the bleach-fixing processing time was 25 seconds) ) Using imagewise exposure, and the following processing steps of 2
Until double replenishment, continuous processing (running test) was performed.

Processing Step Temperature Time Replenisher ^* Color development 38.5 ° C. 45 seconds 73 ml Bleaching and fixing 35 ° C. 25 seconds 60 ml ^** Rinse (1) 35 ° C. 30 seconds-rinse (2) 35 ° C. 30 seconds-rinse ( 3) 35 ° C. for 30 seconds 360 ml Drying 80 ° C. for 60 seconds * Replenishment amount per 1 m ^{2 of} photosensitive material ** In addition to the above 60 ml, 120 ml per 1 m ^{2 of} photosensitive material was poured from rinse (1). (Rinse (3)
From (1) to (3)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g Cowrim chloride 6.5 g-Cowrim bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Fluorescent whitening agent (WHITEX 4 manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0 0.1 g disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g 10.0 g sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-Methyl-4-amino aniline / 3/2 sulfuric acid / 1hydrate 5 Added 0 g 11.5 g Water 1000 ml 1000 ml pH (adjusted with 25 ° C. / potassium hydroxide and sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 600 ml 150 ml sodium thiosulfate 47 g 120 g sodium sulfite 20 g 50 g sodium ethylenediaminetetraacetate (III) 55 g 135 g ethylenediaminetetraacetic acid 5 g 12.5 g nitric acid (67%) 30 g 65 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and NaOH) 5.8 5.6

[Rinse solution] (the tank solution and the replenisher are the same) 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

After the running test, the unexposed color photographic paper was processed and the amount of residual silver was determined to be 15 μg.
/ Cm ² . In the above test, the compounds of the present invention I-2 and II-2 were added to the bleach-fixing solution in a tank solution of 0.1 mol / l, and the replenisher was also added in the same amount of 0.25 mol / l. Similarly, the residual silver content of the color photographic paper after running processing was determined to be 2 μg /
cm ² , and a great improvement in fixability was observed by adding the compound of the present invention.

Example 6 Instead of the undercoated cellulose triacetate film support used for Sample 101 prepared in Example 1, a 10
A sample 201 was prepared in the same manner as in Example 1 except that a substrate having 0 μm polyethylene naphthalate as a support and a stripe magnetic recording tank described in Example 1 of JP-A-4-124628 on the back surface was used. 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 of Example 1 of JP-A-4-62453, and
C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK for protective layer
Example 1 was applied except that was applied at a concentration of 15 mg / m ^2.
A sample 202 was prepared in the same manner as described above. 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.

Example 7 After the completion of the running process of Process No. 21 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 写 Mirror 800 M02-508 〃 Super HG1600 761004 〃 FUJICOLOR 160S 084016 (NSP-120-12)

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 5/38 G03C 7/42

Claims (10)

(57) [Claims] 1. A photographic fixing ability composition comprising at least one compound represented by the following general formula (I). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a hydrogen atom or a cationic group.) 2. A process according to claim 1, wherein a bath having a fixing ability is used in a processing method in which a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support is exposed and then developed. A method for processing a silver halide photographic material, characterized by containing at least one of the compounds represented by the formula (I). 3. The silver halide photographic light-sensitive material according to claim 2, wherein the bath having a fixing ability contains at least one of the compounds represented by the general formula (I) in an amount of 0.01 mol / L or more. Material treatment method. 4. The silver halide photograph according to claim 2, wherein the bath having fixing ability contains thiosulfate ions and further contains at least one of the compounds represented by the general formula (I). Processing method of photosensitive material. 5. A bath having a fixing ability containing thiosulfate ions in an amount of 0.1 mol / liter or more, and further containing at least one of the compounds represented by the above general formula (I) in 0.01%.
3. The composition of claim 2, wherein the content is at least mol / l.
The method for processing a silver halide photographic light-sensitive material described in the above. 6. A process according to claim 1, wherein in a processing method of exposing and developing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, a bath having a fixing ability is used. A method for processing a silver halide photographic light-sensitive material, which comprises at least one of the compounds represented by the formula (I), and is further processed in a washing bath and / or stabilizing bath after processing having a fixing ability. 7. A photographic fixing power composition comprising at least one compound represented by the following general formula (I) and at least one compound represented by the following general formula (II). General formula (I) RSO ₂ SM (wherein, R represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a hydrogen atom or a cationic group.) General formula (II) R′SO ₂ M ′ (In the formula, R ′ represents an aliphatic group, an aromatic group or a heterocyclic group, and M ′ represents a hydrogen atom or a cationic group.) 8. A process according to claim 1, wherein a bath having a fixing ability is used in a processing method in which a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support is exposed and then developed. A method for processing a silver halide photographic light-sensitive material, comprising at least one compound represented by the formula (I) and at least one compound represented by the general formula (II). 9. The bath having a fixing ability contains thiosulfate ions, and at least one of the compound represented by the general formula (I) and at least one of the compounds represented by the general formula (II) according to claim 7. 9. The method for processing a silver halide photographic light-sensitive material according to claim 8, comprising: 10. A method for preparing a replenisher having fixing ability, wherein at least one of the compounds represented by the general formula (I) according to claim 7 and at least one of the compounds represented by the general formula (II) are separately prepared. A method for producing a photographic fixing ability replenishing solution, characterized by adding a solution in which the addition and / or both are added.