JP3442193B2 - Processing method of silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to a processing method which is extremely excellent in fixing speed even when the replenishment rate is low and which is excellent in light fading of the processed light-sensitive material. To provide.

[0002]

2. Description of the Related Art Generally, processing of a silver halide photographic light-sensitive material comprises a developing process, a silver removing process, a washing process and a stabilizing process.
In the silver removal process in color development processing, the developed silver produced in the development process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and is further sensitized by a fixing agent that forms soluble silver together with unused silver halide. Removed from layer (fixed). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. Details of these processing steps are
James, “The Theory of Photog, 4th Edition”
raphic Process "4'th edition) (1977). On the other hand, in order to maintain the processing performance of these various processing steps, a highly active solution called a replenishing solution is added to the processing tank solution. It is general that the tank liquid is partially discharged by such replenishment and is discarded as a so-called overflow liquid.
By the way, due to the recent review of environmental problems on a global scale, it goes without saying that countermeasures are also necessary for such waste liquid problems, and most preferably, it is necessary to reduce these waste liquids as much as possible. is there. In order to reduce the waste liquid, it is considered that the simplest method is to reduce the amount of the above-mentioned replenishing liquid (replenishing amount), but if the replenishing amount of the bath having fixing ability in the present invention is simply reduced, the accumulated components It has been found that the effect of (for example, iodine ions or silver ions eluted from the light-sensitive material) markedly impairs the fixing ability, and at the same time, the photobleaching of the processed light-sensitive material significantly deteriorates. This problem also occurs when thiosulfate, which is a fixing agent that has been widely used in the past, is used, or when thiones described in JP-A-6-51455 are used instead of thiosulfate. It turned out to be worse, and the solution was hoped for.

[0003]

Therefore, the first aspect of the present invention
An object of the present invention is to provide a processing composition having excellent fixability and a processing method using the same. A second object of the present invention is to provide a processing method with excellent photofading properties.

[0004]

In the present invention, as a result of various studies, it was found that the above object can be achieved by the following method. (Item 1) After developing a silver halide photographic light-sensitive material,
In the desilvering processing method, a processing bath having a fixing ability in the desilvering step contains both a thiosulfate group and a compound represented by the following general formula (I) in a molar ratio of 1: 0.05 to 1: 0.30. A method of processing a silver halide photographic light-sensitive material, comprising:

[0005]

[Chemical 2]

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group. However, at least one of R ¹ , R ² , R ³ and R ⁴ represents an alkyl group substituted with a sulfonic acid or a salt thereof, or a carboxylic acid or a salt thereof. The total carbon number of the compound represented by formula (I) is 2 to 4. (Item 2) The bath having the above fixing ability is 0.003 to 0.0
A method for processing a silver halide photographic light-sensitive material, which comprises 3 mol / liter of iodine ion. (Item 3) A method of processing a silver halide color photographic light-sensitive material, wherein the bath having the fixing ability of item 2 is a bleach-fixing solution. (Item 4) The replenishing amount of the bath having the fixing ability of Item 2 is 100.
A method for processing a silver halide color photographic light-sensitive material, characterized in that it is ˜550 ml / square meter. (Item 5) The method for processing a silver halide color photographic light-sensitive material according to Item 1 or 2, wherein the light-sensitive material has a magnetic recording layer. The above-mentioned thiourea compound of the general formula (I) is exemplified in JP-A-6-51455 as a fixing agent in place of the thiosulfate group, and the thiourea compound having a total carbon number of 5 or more has a fixing ability. JP-A-3-2138 as a liquid stabilizer
No. 54 is exemplified. However, in the present invention, under the condition that the replenishing amount of the bath having fixing ability is reduced or the iodine ions are accumulated, there is a problem that the fixing ability is decreased and at the same time, photobleaching of the light-sensitive material is deteriorated. It turned out that In the present application, the total carbon number is 2 to 4
In addition, it is totally unexpected that the fixing speed was significantly accelerated under such conditions for the first time by using a thiourea compound substituted with a sulfonic acid or a carboxylic acid and a thiosulfate group in a specific ratio. Met.

Next, the general formula (I) of the present invention will be described in detail. In the general formula (I), R ¹ , R ² , R ³ and R
Each of ⁴ represents a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, isopropyl group, sulfoethyl group, hydroxyethyl group, aminoethyl group, etc.). Also,
R ² and R ⁴ may form a ring, and examples thereof include an imidazoline-2-thione ring.

Further, these alkyl groups may be substituted. The following are mentioned as a substituent. Representative substituents include, for example, a methyl group, a methoxy group,
Examples thereof include a methanesulfonylamino group, a sulfonyl group, a sulfinyl group, a methylthio group, a cyano group, a nitro group and a hydroxyl group. When there are two or more substituents, they may be the same or different. However, at least one of R ¹ , R ² , R ³ and R ⁴ is sulfonic acid or a salt thereof (for example, alkali metal salt, ammonium salt), carboxylic acid or a salt thereof (for example, alkali metal salt, ammonium salt). Be replaced with.

The general formula (I) preferably represents the following general formula (II). General formula (II)

[0010]

[Chemical 3]

In the general formula (II), R ⁵ is at least one sulfonic acid or a salt thereof (for example, an alkali metal salt,
Ammonium salt), an alkyl group (eg, sulfomethyl group, sulfoethyl group) substituted with a carboxylic acid or a salt thereof (eg, alkali metal salt, ammonium salt),
Carboxymethyl group, carboxyethyl group, sulfopropyl group, 2-methylsulfoethyl group, 2-carboxyethyl group, etc.), and preferably one sulfonic acid or a salt thereof (eg, alkali metal salt, ammonium salt).
Is a substituted alkyl group.

The most preferred total carbon number of the compounds represented by the general formula (I) and the general formula (II) is 2 and 3. Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

The compound represented by formula (I) of the present invention can be prepared by a known method, for example, Journal of Organic Chemicals.
Chemistry (J. Org. Chem.) 24, 470-473.
(1959), Journal of Heterocyclic Chemistry (J. Heterocycl. Chem.) 4,605-6.
09 (1967), "Pharmaceutical magazine" 82, 36-45 (196
2), JP-B-39-26203, JP-A-63-229
It can be synthesized with reference to No. 449 and OLS-2,043,944. The above compound is used in a fixing solution or a bleach-fixing solution in combination with thiosulfate, and the molar ratio is 0.05 to 0.3, preferably 0.07 to thiosulfate.
0.25, more preferably about 0.10 to 0.20 is used. The specific amount of addition, of course, varies depending on the amount of thiosulfate used, but is about 0.001 mol to 0.5 mol / liter, and more preferably about 0.05 mol to 0.3 mol / liter. Two or more kinds of the compounds of the general formula (I) of the present invention may be used, but in the case of using a plurality of kinds, the total addition amount thereof needs to be within the range of the ratio with the thiosulfate group. Is. The details of the fixing bath of the present invention will be described later.

The treating agent applicable to the present invention may be supplied as a concentrated liquid having a single or plural parts, or may be supplied in the form of powder, tablets, granules, paste and the like.
Also, it may be supplied in the form of a used liquid, such as a concentrated liquid, a powder, a tablet,
It may be an arbitrary combination of granules, paste and used liquid. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, etc. are used alone or as a composite material in a container for accommodating these treating agents. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for a container, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less. In the case of a single concentrate, it is diluted and used as a replenisher. In this case, it is preferable to automatically dilute the replenisher tank with water by setting a concentrated solution in the developer. It is preferable to use the water in the wash water replenishment tank as this water. Alternatively, the concentrated liquid may be directly replenished to the treatment tank, and water corresponding to the dilution rate may be directly replenished to the treatment tank. Especially, it is preferable in a compact developing machine having no replenishing tank. The same applies to the concentrated solution having a plurality of parts, and it is preferable to automatically dilute the concentrated solution in the replenisher tank with water by setting the concentrated solution in the developing machine. It is preferable to use the water in the wash water replenishment tank as this water. Further, the treatment tank may be directly replenished for each part, and water corresponding to the dilution rate may be directly replenished to the treatment tank. Also,
Similarly, in the case of powders, tablets, granules, and paste-like treatment agents, it is also preferable to add the chemicals directly to the treatment tank and at the same time add water in proportion to the dilution rate to the treatment tank. It is also preferable that the solution is automatically dissolved and diluted in the replenishment tank and used as a replenisher.

Next, the processing method of the present invention will be described in detail focusing on the processing of the color light-sensitive material. The color developing solution (color developing solution) used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 mol, per liter of the color developing solution.
It is 0.1 mol. Color developing solutions include hydroxylamine, diethylhydroxylamine, and JP-A-3-14.
Hydroxylamines represented by the general formula (I) of No. 4446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl
-3-Auxiliary developing agents such as pyrazolidone, tackifiers,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimino Diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxy) Representative examples thereof include phenylacetic acid) and salts thereof.

Of the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, N-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
Examples include diethylhydroxylamine.

If desired, any antifoggant can be added to the color developer used in the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention has a preferable pH range of about 9.5 to 10.5. If the developing activity can be maintained, it is preferable that the pH of the developing tank liquid is low also in the sense of preventing the generation of ammonia gas from the waste liquid. The most preferable pH of the tank liquid is 9.9 to 1
It is about 0.4. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate,
Phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino Butyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. The use of carbonate is particularly preferable. The amount of the buffer added to the developer is
It is preferably 0.1 mol / liter or more, and particularly
It is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-
146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841
Examples thereof include chelating agents described in German Patent No. 3739610, European Patent No. 468325, and the like. It is preferable that the processing solution in the replenishing tank of the color developing solution or the processing tank is shielded with a liquid agent such as a high boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. Further, it is particularly preferable to use it for a replenishment tank. The processing temperature of the color developing solution in the present invention is 30 to 55 ° C, preferably 35 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds in the light-sensitive material for photography. The replenishing amount is 30 to 800 ml, preferably 50 to 50, per square meter of the light-sensitive material.
It is about 0 ml.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. Any development accelerator can be added to the developer used in the present invention, if necessary. As a development accelerator, Japanese Patent Publication No. 37-16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, U.S. Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. next,
The desilvering process of the present invention will be described in detail. The desilvering process generally has a bleaching process, a bleach-fixing process, and a fixing process, and there are various processes. Specific steps are shown below, but the invention is not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-bleach-fixing (step 3) Bleach-bleach-fixing-fixing (step 4) Fixing-bleach-fixing (step 5) Bleach-fixing In the present invention, a bleach-fixing solution. Steps 1 and 2 using
Cases of 3 and 4 are preferable. Especially when the technique of the present invention is applied to a bleach-fixing solution, the desilvering performance is remarkably improved, and at the same time, the light-fading property of the light-sensitive material is also improved.

As the bleaching agent used in the processing solution having bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, red blood salt and the like are used. The polycarboxylic acid (III) complex can be most preferably used. The ferric complex salt used in the present invention is
It may be added as a complexed iron complex salt in advance and dissolved, or a complexing compound and a ferric salt (for example, ferric sulfate, ferric chloride, ferric bromide, iron nitrate (III ), Iron (III) sulfate ammonium, etc.) to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when added in an excess amount, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

In the present invention, the compound forming a ferric complex salt in a liquid having a bleaching ability is ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the bleaching treatment solution of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
It is preferably in the range of liter, more preferably 0.02.
The range is from 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is
The amount is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, compounds having a mercapto group or a disulfide bond described in US Pat. No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630 and Research Disclosure 17129 (July 1978). Alternatively, halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acids and organic acids having a buffering capacity and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution and the fixing agent component in the fixing solution are
The aforementioned thiosulfate and the compound of general formula (I) are used. Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate and the like. Other known fixing agents, thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble salts such as mesoions. It is a silver halide dissolving agent, and these may be used alone or in combination of two or more. In the present invention, it is preferable to use thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate. The total amount of the fixing agent per liter is preferably 0.3 to 3 mol, more preferably 0.5 to 2.0 mol. The processing liquid having fixing ability of the present invention preferably contains at least one compound represented by the following general formula (III) or general formula (IV) in the sense that the desilvering property and the image storability are improved. General formula (III)

[0032]

[Chemical 8]

In the formula, R represents a substituent of the benzene ring, and n represents an integer of 0-6. When n is 2 or more, R
May be the same or different. Preferred substituents include
It represents an alkyl group having 1 to 3 carbon atoms, a substituted alkyl group, an alkoxy group, a hydroxyl group, a nitro group, a carboxylic acid, a sulfonic acid, a halogen atom, a phosphonic acid, or the like. As the substituent of the alkyl group, a hydroxy group, carboxylic acid, sulfonic acid and the like are preferable. M represents a hydrogen atom, an alkali metal, an alkaline earth, ammonium, or an amine. Specific examples of preferred compounds represented by formula (III) are shown below, but the invention is not limited thereto.

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

General formula (IV) R-SO ₂ M In the general formula (IV), R represents an alkyl group, preferably having 1 to 30 carbon atoms, particularly 1 to 20 straight chain, branched or Cyclic alkyl groups (eg, methyl, ethyl,
Isopropyl, n-propyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,
Examples include cyclopentyl, cecrohexyl, etc., alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (eg, piropagyl, 3-pentynyl, etc.), aralkyl groups (eg, benzyl, etc.).

The alkyl group represented by R in the general formula (IV) may have a substituent, and examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.). , Alkyl groups (eg methyl, ethyl, iso
-Propyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl etc.), alkenyl group (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), aralkyl. Group (eg benzyl, phenethyl etc.), aryl group (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic group (eg pyridyl, furyl, imidazolyl, piperidyl, morpholyl etc.), alkoxy group (eg methoxy, ethoxy, butoxy). etc),
Aryloxy group (eg phenoxy, 2-naphthyloxy etc.), amino group (eg unsubstituted amino, dimethylamino, ethylamino, anilino etc.), acylamino group (eg acetylamino, benzoylamino etc.), ureido group (eg unsubstituted Ureido, N-methylureido,
N-phenylureido etc.), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino etc.), sulfonylamino group (eg methylsulfonylamino, phenylsulfonylamino etc.), sulfamoyl group (eg unsubstituted sulfamoyl group, N, N-dimethyl) Sulfamoyl, N-phenylsulfamoyl, etc.), carbamoyl group (eg, unsubstituted carbamoyl,
N, N-diethylcarbamoyl, N-phenylcarbamoyl etc.), a sulfonyl group (eg mesyl, tosyl etc.),
Sulfinyl group (eg methylsulfinyl, phenylsulfinyl etc.), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl, formyl, pivaloyl etc.) , An acyloxy group (eg acetoxy, benzoyloxy etc.), a phosphoric acid amide group (eg N, N-diethyl phosphoric acid amide etc.), an alkylthio group (eg methylthio, ethylthio etc.), an arylthio group (eg phenylthio etc.), a cyano group , Sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (for example, trimethylammonio), phosphonio group, Dorajino group, and the like. When there are two or more substituents, they may be the same or different.

In the general formula (IV), M represents a hydrogen atom or an unsubstituted ammonium group or an alkali metal or alkaline earth metal substitution, and the alkali metal is lithium,
Examples of sodium, potassium and alkaline earth metals include calcium and barium, but more preferred are sodium and unsubstituted ammonium.

Specific examples of the compound represented by formula (IV) are shown below, but the invention is not limited thereto.

[0042]

[Chemical 13]

These compounds are disclosed, for example, in JP-A-62-14.
3048 Publication, Journal of Organic Chemistry (J. Org. Chem.) Volume 7, 23-
30 (1942), The Chemistry of sulphinic acid, estersan
d their derivatives) Patay Series Editor
(PATAI Series Editor) (1990), etc. for easy synthesis. The amount of these compounds added is 0.01 to 2 mol, preferably 0.05 to 2 mol, per liter of the treatment liquid.
It is 1 mol. The bleach-fixing solution and the fixing solution of the present invention preferably contain a sulfite (or bisulfite or metabisulfite) as a preservative, but especially from 0.03 to
0.5 mol / liter, more preferably 0.05 to 0.
It is preferable to contain 3 mol / liter. The bleach-fixing solution and the fixing solution of the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as preservatives. In addition to containing sulfite ion-releasing compounds such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite), aldehydes (benzaldehyde, acetaldehyde, etc.), ketones (acetone, etc.) , Ascorbic acids, hydroxylamines, benzenesulfinic acids, alkylsulfinic acids and the like can be added as necessary. The bleaching solution, the bleach-fixing solution, and the iodide ion contained in the fixing solution used in the present invention are preferably 0.003 to 0.03 mol / liter, and more preferably 0.005 to 0.02 mol / liter. In this range, the desilvering property is remarkably promoted.

Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferable pH range is 4-8.
And more preferably 4.5 to 6.5. The bleaching solution, the bleach-fixing solution, and the replenishing amount to the fixing solution used in the present invention are preferably 50 to 2000 ml per 1 m ² of the light-sensitive material. More preferably, the effect of the present invention can be remarkably exhibited when the replenishing amount of the bath having fixing ability is 100 to 550 ml. Further, after-wash water such as washing water or overflow solution of the stabilizing bath may be replenished if necessary. The replenishment amount in the present invention represents the total amount of the replenished substance, and the replenished substance may be a so-called replenishing liquid, “concentrated liquid + water”, or “solid replenisher + water”. good. The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak Company issued Z-121, Eusing Process C-41 3rd
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment. When the present invention is applied to a black-and-white light-sensitive material, it may be used according to the above-mentioned fixing solution.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the
Society of Motion Pictureand Television Engineers
It can be determined by the method described in Volume 64, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. In addition, JP-A-57
-8,542 isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, sterilization and antifungal technology of microorganisms" edited by the Society for Hygiene Technology (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1986)
It is also possible to use the bactericide described in.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1). , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferred because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A No. 1-231051. ..

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect. It is preferable to add various chelating agents to the wash water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ′, N′-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized, and water is replenished in the bleaching tank in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645 and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Next, the light-sensitive material of the present invention will be described.
The present invention can be applied to any light-sensitive material (for example, color, black and white) having the above-mentioned transmission support, but is preferably applied to a color negative film and a color reversal film. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are Those described in the following patent publications, in particular, EP 0,355,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

The silver halide emulsion used in the present invention is
Silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide,
Emulsions of various halogen compositions such as silver chloride can be used. In particular, the present invention preferably has a layer containing a silver iodobromide emulsion and has an iodine content of 1.0 to 10
It is preferable to use an emulsion containing about mol%. As the coating amount of silver is not particularly limited, 2g~10g / m ² approximately, and more preferably may contain about 3 to 8 g / m ^2. The light-sensitive material used in the present invention may contain various couplers, but the details are as shown in Table 2. Further, as a cyan coupler, Japanese Patent Application Laid-Open No. 2-3314
In addition to the diphenylimidazole type cyan couplers described in No. 4, 3-hydroxypyridine type cyan couplers described in European Patent EP0,333,185A2 (among others, the coupler (42) listed as a specific example is a 4-equivalent coupler with chlorine. Those having a leaving group and made into two equivalents, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (among others, listed as specific examples). (Coupler Examples 3, 8, 34 are especially preferred).

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP0,337,490A2, pages 27 to 76 for the purpose of improving the sharpness of an image. Such dyes (among others, oxonol dyes) can be added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more. In the color photographic light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with the aromatic amine type developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably. In the present invention, the case where the dry film thickness of the silver halide photographic light-sensitive material excluding the support is 25 μm or less is preferable in the sense that the carryover amount is reduced and the silver recovery rate is increased. In particular, about 13 to 23 μm, more preferably 9
It is preferably about 19 μm. These film thicknesses can be reduced by reducing the gelatin amount, silver amount, oil amount, coupler amount, etc., but it is most preferable to reduce the gelatin amount. Here, the film thickness of the sample is 25 ° C., 60R
H% can be measured by an ordinary method after being left for 2 weeks.
In the silver halide photographic light-sensitive material used in the present invention, it is preferable that the photographic layer has a film swelling degree of 1.5 to 4.0 from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The degree of swelling in the present invention means that the photosensitive material is 3
A value obtained by dividing the film thickness of the photographic layer after dipping in distilled water at 3 ° C. for 2 minutes by the film thickness of the dried photographic layer.

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

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are used.

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

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved. The processing method of the present invention can be applied to various light-sensitive materials. Especially color negative film, color reversal film, film negative film,
Examples thereof include positive films for motion pictures, but application to color negative films is particularly preferable. As described above, the present invention has a larger film thickness than the black-and-white light-sensitive material, has a large amount of coated silver, and is particularly effective in the desilvering process of a color light-sensitive material containing various couplers, oils and the like. Here, the color negative film preferably uses the emulsion having the above-mentioned halogen composition, and preferably has the above-mentioned coated silver amount. As the light-sensitive material used in the present invention, the following materials can be preferably used. A light-sensitive material having a magnetic recording layer, which comprises magnetic particles (preferably Co-coated ferromagnetic iron oxide) dispersed in a binder and is optically transparent. Is preferably provided on the entire surface of. The magnetic particles may be treated with a coupling agent as described in JP-A-6-161032. As the binder, the polymers described in JP-A-4-219569 can be preferably used. Also,
This recording layer may be provided anywhere, but it is preferably provided on the side opposite to the emulsion layer (back layer) with respect to the support. It is preferable that a layer containing a slipping agent is provided on the recording layer, and a matting agent is contained in the outermost layer on the side of the photosensitive emulsion layer with respect to the support. Further, the photosensitive material preferably contains an antistatic agent in order to impart antistatic properties even after development processing, and as the antistatic agent, a conductive metal oxide or an ionic polymer is preferred. . Antistatic agents are
Electric resistance of 25 degrees, 10% RH, 10 ¹² Ω · cm
It is preferable to use it as follows. US Pat. No. 5,336,58 discloses a photosensitive material having a magnetic recording layer.
9, 5,250,404, 5,229,259, 5,215,874, and EP 466130A. Further, as the support used for the photosensitive material,
A polyester support having improved curl and having a thin layer is preferred. The thickness is preferably from 50 to 105 μm, and the material is preferably a polyethylene aromatic dicarboxylate-based polyester (preferably one containing benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol as the main raw materials). The glass transition temperature is preferably 50 to 200 degrees. Further, as the surface treatment of the support, ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment and flame treatment are preferable. Further, it is preferable to perform heat treatment for 0.1 to 1500 hours in the range of 40 ° C. to the glass transition temperature of the support before or after applying the undercoat layer to the support and before coating the emulsion layer. In addition to support, photosensitive material, development processing,
For cartridges etc., open technical report, public skill number 94
-6023 (published by the Institute of Invention and Innovation, 1994).

[0066]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (1) Support Material, etc. The support used in this example was prepared by the following method.・ TAC: Methylene chloride / methanol = 82/8 wt by a normal solution casting method of triacetyl cellulose
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used.

(2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment on both sides thereof, and then an undercoat liquid having the following composition was applied to provide the undercoat layer on the high temperature surface side during stretching. . For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. Discharge frequency during treatment is 9.6KHz, gap clearance between electrode and dielectric roll is 1.6mm
Met.

[0068]   Gelatin 3g   250 ml of distilled water   Sodium-α-sulfodi-2-ethylhexyl succinate 0.05g   Formaldehyde 0.02g   Further, an undercoat layer having the following composition was provided on the support TAC.   Gelatin 0.2g   Salicylic acid 0.1g   15 ml of methanol   85 ml of acetone   Formaldehyde 0.01g

(3) Coating of Back Layer The following back layers 1 to 3 were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing acicular γ-iron oxide fine powder (containing as gelatin dispersion; average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ² described in the following chemical formula 14. 0.1 g / m ² Compound described in Chemical formula 15 below 0.02 g / m ² Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[0070]

[Chemical 14]

[0071]

[Chemical 15]

(B) Back second layer Gelatin 0.05 g / m ² conductive material [S _n O ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² dodecylbenzenesulfone Acid soda 0.05g / m ²

C) Third layer of back gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound shown by the following chemical formula 16 0.01 g / m ²

[0074]

[Chemical 16]

The coercive force of the obtained back layer is 960 Oe.
Met.

(4) Heat Treatment of Support By the above method, the undercoat layer and the back layer were applied, dried and wound, and then heat-treated at 110 ° C. for 48 hours.

(5) Preparation of Photosensitive Layer Each layer having the composition shown below was coated in multiple layers to prepare each sample as a color negative film. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Hardening agent ExS: Number corresponding to each component of the sensitizing dye indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0093]

[Table 6]

In Table 6, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of 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 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate and 5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) (0.5 g) were put in a 700 ml pot mill, and the dye was added. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. 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 of the dye. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0097]

[Chemical 17]

[0098]

[Chemical 18]

[0099]

[Chemical 19]

[0100]

[Chemical 20]

[0101]

[Chemical 21]

[0102]

[Chemical formula 22]

[0103]

[Chemical formula 23]

[0104]

[Chemical formula 24]

[0105]

[Chemical 25]

[0106]

[Chemical formula 26]

[0107]

[Chemical 27]

[0108]

[Chemical 28]

[0109]

[Chemical 29]

[0110]

[Chemical 30]

[0111]

[Chemical 31]

[0112]

[Chemical 32]

The light-sensitive material prepared as described above is used for 35 mm
The width was cut into 110 cm. Next, the details of the performed processing will be described. The above sample is 10 cms at a color temperature of 4800K.
Was exposed in a stepwise manner and processed by the cine type automatic developing machine with the following processing steps and processing solutions. Incidentally, the fixing solution was changed in additives as shown below, and each of them was sequentially processed.

(Processing step) Process processing time Processing temperature Color development 3 minutes 15 seconds 38.0 ℃ Bleach 45 seconds 38.0 ℃ Fixed arrival 1 minute 00 seconds 38.0 ℃ Stability (1) 20 seconds 38.0 ℃ Stability (2) 20 seconds 38.0 ℃ Stability (3) 20 seconds 38.0 ℃ Dry 1 minute 55 ℃ * Stable countercurrent method from (3) to (1)

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g)       Diethylenetriamine pentaacetic acid 5.0       Sodium sulfite 4.0       Potassium carbonate 30.0       Potassium bromide 1.4       Potassium iodide 1.2 mg       Hydroxylamine sulfate 2.4       N, N- (disulfonatoethyl) hydro           Xylamine 5.0       4- [N-ethyl-N- (β-hydroxyethyl) amino]-         2-methylaniline sulfate 4.5       1.0 liter with water       pH (adjusted with potassium hydroxide and sulfuric acid) 10.10

[0116] (Bleaching solution) Tank solution (g)       1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate                                           150.0       1,3-diaminopropanetetraacetic acid 3.0       Ammonium bromide 100.0       Ammonium nitrate 17.5       Ammonia water (27%) 10.0       Acetic acid (98%) 50.0       Potassium carbonate 10.0       1.0 liter with water       pH (adjusted with aqueous ammonia and acetic acid) 4.3

[0117] (Fixer) (Unit: g)       Ethylenediaminetetraacetic acid disodium salt 1.7       Sodium sulfite 16.0       Sodium bisulfite 11.0       Ammonium thiosulfate aqueous solution (700 g / liter)                                           See Table 7       Refer to Table 7 for compounds of general formula (I)       Ammonium iodide See Table 7       Silver bromide 5.0       1.0 liter with water       pH 6.5

(Stabilizer) (Unit: g) Surfactant 1.0 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] Polymaleic acid (average molecular weight 2000) 1.0 1,2-Benzisothiazoline-3 The amount of residual silver in the unexposed area of the sample treated with each fixing solution having a composition of 1.0 liter and pH 8.5 with the addition of -ON 0.05 water was measured by fluorescent X-ray. Also, 7500
Irradiation was performed with 0 Lux of xenon light for 24 hours, and the amount of density decrease at the exposure point of 2.0 was measured with magenta density. The results are shown in Table 7.

[0119]

[Table 7]

The structures of comparative compounds A, B and C in Table 7 are shown below.

[0121]

[Chemical 33]

From Table 7, in the present invention, the desilvering (fixing) performance is excellent, and the photofading of the magenta dye is also improved. Especially, the iodine ion is 0.003 to 0.03 mol /
When it was in liter, the desilvering property and the fading performance showed the best results.

Example 2 The sample (photosensitive material) described in Example 1 was subjected to continuous processing (running test) after imagewise exposure in the following processing steps until it was replenished with twice the tank capacity for color development. went. However,
The following three formulations A, B and C were used for the bleach-fix bath, and the replenishment amount was changed as shown in Table 8, and a running test was conducted for each of them. The processing steps are shown below. (Processing process) Processing process Temperature Time Replenishment amount * Color development 45 ℃ 90 seconds 260 Bleaching fixing 40 ℃ 90 seconds Table 8 Stability (1) 40 ℃ 15 seconds-Stability (2) 40 ℃ 15 seconds-Stability ( 3) 40 ℃ 15 seconds 390 Dry 75 ℃ 30 seconds- (Stable is the three-tank counter-current method from (3) to (1).) * Per square meter. (ML) The carry-on amount from the front bath is 6 per 1 square meter of light-sensitive material.
It was 0 ml.

The composition of each processing liquid is as follows. (Color developer) (Unit: g)                                         Tank liquid replenisher       Diethylenetriamine pentaacetic acid 4.0 4.0       4,5-dihydroxybenzene-1,3-           Disulfonic acid disodium salt 0.5 0.5       Sodium sulfite 4.0 8.0       Potassium carbonate 38.0 38.0       Potassium bromide 4.0 −       Potassium iodide 1.3 mg −       N, N-di (sulphonate         Ethyl) hydroxylamine 5.0 10.0       2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl)         Amino] aniline sulfate 10.0 22.0       1.0 liter with water added 1.0 liter         pH (adjusted with potassium hydroxide and sulfuric acid)                                            10.05 10.40

[0125] (Bleaching Fixing Solution A) (Comparative Example) (Unit: g)                                             Tank liquid replenisher       Ethylenediamine- (2-carboxy       Phenyl) -N, N ', N'-triacetic acid 0.10 mol 0.12 mol       Ethylenediaminetetraacetic acid 0.06 mol 0.08 mol       Ferric chloride 0.16 mol 0.18 mol       Ammonium thiosulfate 1.5 mol 1.6 mol       Ammonium iodide 1.0 −       Ammonium sulfite 10.0 40.0       Succinic acid 12.0 12.0       1.0 liter with water added 1.0 liter       pH (adjusted with nitric acid and ammonia water) 5.5 5.0

[0126] (Bleaching Fixing Solution B) (Comparative Example) (Unit: g)                                             Tank liquid replenisher       Ethylenediamine- (2-carboxy       Phenyl) -N, N ', N'-triacetic acid 0.10 mol 0.12 mol       Ethylenediaminetetraacetic acid 0.06 mol 0.08 mol       Ferric chloride 0.16 mol 0.18 mol       Compound I-3 1.5 mol 1.6 mol       Ammonium iodide 1.0 −       Ammonium sulfite 10.0 40.0       Succinic acid 12.0 12.0       1.0 liter with water added 1.0 liter       pH (adjusted with nitric acid and ammonia water) 5.5 5.0

[0127] (Bleach-fixing solution C) (invention) (unit: g)                                             Tank liquid replenisher       Ethylenediamine- (2-carboxy       Phenyl) -N, N ', N'-triacetic acid 0.10 mol 0.12 mol       Ethylenediaminetetraacetic acid 0.06 mol 0.08 mol       Ferric chloride 0.16 mol 0.18 mol       Compound I-3 0.25 mol 0.30 mol       Ammonium thiosulfate (pure) 1.25 1.30       Ammonium iodide 1.0 −       Ammonium sulfite 10.0 40.0       Succinic acid 12.0 12.0   1.0 liter with water added 1.0 liter   pH (adjusted with nitric acid and ammonia water) 5.5 5.0

[0128] (Stabilizer) Tank liquid and replenisher have the same formulation                                           (Unit: g)       Polyoxyethylene-p-monononylphenyl ether          (Average degree of polymerization 10) 0.2       Chlorinated sodium isocyanurate 0.02       Deionized water (conductivity 5μs / cm or less)                                          1000 ml         pH 6.5

The running equilibrium solution of each bleach-fix solution is
Iodine ion concentrations were analyzed using an ion chromaro.
Further, the sample was exposed to 10 CMS through a wedge wedge and then treated with a treatment solution which reached each running equilibrium, and the maximum concentration part of the treated sample was determined by a fluorescent X-ray for the amount of residual silver. . At the same time, the photobleaching of magenta was measured in the same manner as in Example 1. The results are shown in Table 8.

[0130]

[Table 8]

In the bleach-fixing solution C of the present invention in which the thiosulfate group and the compound of the general formula (I) of the present invention are used in combination, both desilvering performance and photobleaching are remarkably improved, and especially the replenishing amount is from 100 to
The best results were obtained in the range of 550 ml / square meter.

Example 3 In Example 2, No. Compound I-under the same conditions as 44
Instead of 3, I-1, I-2, I-6, and I-11
When each of them was similarly subjected to running processing, it exhibited excellent desilvering performance and photofading performance.

Example 4 No. 2 of Example 2. Under the same conditions as 33, 39, 45,
However, the running test was carried out by changing the composition of the bleach-fixing solution as follows. (Bleach-fixing solution A1) Same as bleach-fixing solution A except that 0.15 mol / liter of compound III-2 was added to both tank solution / replenishing solution of bleach-fixing solution A. (Bleach-fixing solution A2) Same as bleach-fixing solution A except that 0.15 mol / l of compound III-3 was added to both tank solution / replenishing solution of bleach-fixing solution A. (Bleach-fixing solution B1) Same as bleach-fixing solution B except that 0.15 mol / liter of compound III-2 was added to both tank solution / replenishing solution of bleach-fixing solution B. (Bleach-fixing solution B2) Same as bleach-fixing solution B except that 0.15 mol / liter of compound III-3 was added to both tank solution / replenishing solution of bleach-fixing solution B. (Bleach-fixing solution C1) Same as bleach-fixing solution C except that 0.15 mol / liter of compound III-2 was added to both tank solution / replenishing solution of bleach-fixing solution C. (Bleach-fixing solution C2) Same as bleach-fixing solution C except that 0.15 mol / liter of compound III-3 was added to both tank solution / replenishing solution of bleach-fixing solution C.

Table 9 shows the results of evaluation of desilvering property and photobleaching in the same manner as in Example 2.

[0135]

[Table 9]

According to the present invention, the desilvering performance and the fading of magenta are improved, but the particularly preferred general formula (III) of the present invention is
Alternatively, the most preferable result is shown in the bleach-fixing solution using the compound of the general formula (IV).

[0137]

EFFECT OF THE INVENTION It is possible to form an image which is excellent in fixing property and photofading property. In particular, these effects can be effectively achieved even when the amount of iodine ions in the fixer or the bleach-fixer is large. Further, by using the compounds together in the proportions as in the present invention, it is possible to process a silver halide light-sensitive material excellent in fixing property and photofading. This effect is particularly remarkable in the case of a color light-sensitive material.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-46-3340 (JP, A) JP-A-58-122536 (JP, A) JP-A-61-183645 (JP, A) JP-A-1- 154154 (JP, A) JP-A-3-213854 (JP, A) JP-A-6-51455 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/42 G03C 5 / 38

Claims (5)

(57) [Claims] 1. In a processing method of desilvering a silver halide photographic light-sensitive material after development, a thiosulfate group and a compound of the following general formula (I) are added to a processing bath having fixing ability in the desilvering step. A processing method for a silver halide photographic light-sensitive material, characterized in that both are contained in a molar ratio of 1: 0.05 to 1: 0.30. General formula (I) In general formula (I), R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an alkyl group. However, R ¹ , R
^At least one of ² , R ³ and R ⁴ represents an alkyl group substituted with a sulfonic acid or a salt thereof, or a carboxylic acid or a salt thereof. The total carbon number of the compound represented by formula (I) is 2 to 4. 2. A bath having the above fixing ability is from 0.003 to
2. The method for processing a silver halide photographic light-sensitive material according to claim 1, which contains 0.03 mol / liter of iodide ion. 3. The method for processing a silver halide photographic light-sensitive material according to claim 2, wherein the bath having fixing ability according to claim 2 is a bleach-fixing solution. 4. The method of processing a silver halide photographic light-sensitive material according to claim 2, wherein the replenishing amount of the bath having fixing ability is 100 to 550 ml / square meter. 5. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material has a magnetic recording layer.