JPS612149A - Treatment of silver halide photographic material - Google Patents

Abstract

PURPOSE:To reduce the amt. of water necessary for washing and to improve the stability of picture image in the stage of developing and fixing an exposed silver halide photographic material by washing with aq. soln. contg. a chelating agent succeeding to a treatment using thiosulfate. CONSTITUTION:After developing an exposed silver halide photographic material, the material is subjected to fixing or bleach-fix treatment for the purpose of desilvering with a treating soln. contg. thiosulfate. Then, the material is washed with aq. soln. contg. a chelating agent to wash off thiosulfate from the photosensitive material. Specific examples for the chelating agent are sodium tripolyphosphate, ethylenediamine tetraacetic acid, nitrilo triacetic acid, etc., and the suitable amt. thereof to be used is about 0.01-50g per 1l washfing soln. By this process, generation of precipitate in the water washing tank due to decomposition of thiosulfate is prevented, and sufficient washing with small amt. of water is possible.

Description

Detailed Description of the Invention [Technical Field] The present invention relates to a method for processing silver halide photographic materials, and more particularly to a method for processing silver halide photographic materials, and more specifically, a method for processing silver halide photographic materials that can significantly reduce the amount of washing water in the washing step after the processing step containing thiosulfate. It relates to a method of processing photographic materials.

<Background of the Invention> Generally, after exposure, silver halide photographic materials are processed through a process of development, fixed-fixing and water-washing, or development-bleaching, fixed-fixing and washing with water. In recent years, environmental conservation issues have arisen regarding this type of treatment.
Also, water resource issues are becoming more important. For this reason, methods have been proposed to reduce the amount of washing water used in large quantities; for example, in West German Patent No. 2,920,222,
A technique is described in which the water washing tank is configured in multiple stages to cause water to flow backwards.

However, if the washing water following the thiosulfate-containing bath is greatly reduced by configuring the tank in multiple stages, the residence time of the washing water will become longer and the thiosulfate will decompose. It has been found that another problem arises in that sulfide precipitation occurs. If this precipitate adheres to the photographic material being processed, it will seriously affect the photographic processing performance, so the washing tank must be periodically cleaned to remove it.

In order to eliminate such drawbacks, a method for preventing sulfide precipitation in the water washing process is proposed, for example, in US Pat. No. 4,055.
No. 9,446 introduces a technique of adding a polyalkylene oxide nonionic surfactant to a water washing bath.

However, even if these nonionic surfactants are added to the entire wash water, they do not prevent the occurrence of sulfide precipitation, and not only do they only slightly disperse the precipitates, but they also cause foam to form in the wash bath. Therefore, it is difficult to put it into practical use. In addition, the biggest drawback of these technologies is that the image stability after processing is poor; for example, when color prints are stored for a long period of time, yellow stains may occur on the white background of unexposed areas, and cyan dye density may decrease. It is to let

<Object of the Invention> An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material, which makes it possible to significantly reduce the amount of washing water without affecting photographic performance. Another object of the present invention is to provide a water washing process that improves the stability of images, especially after processing.

<Description of the Invention> After exposure, a silver halide photosensitive material subjected to color development is processed with a processing solution containing thiosulfate.

In the present invention, this is followed by treatment with an aqueous solution containing a chelating agent.

The processing step using a processing solution containing thiosulfate of the present invention refers to a step using a fixing bath, a bleach-fixing bath, etc. for the purpose of desilvering silver halide photographic materials, and thiosulfate is a silver complex. used as a curing agent. The purpose of the subsequent processing step is to wash out the thiosulfate from the photosensitive material, and in the present invention, the processing tank structure is divided into multiple tanks, and the amount of washing water is reduced by incorporating a chelating agent into the processing solution. significantly reduced. The number of tanks for this treatment process is 2 or more.
It is preferable that the number of tanks is higher than the number of washing tanks.
Can be reduced. Furthermore, at this time, it is preferable to use a so-called countercurrent method in which the processing liquid flows back from the rear bathtub to the front bathtub.

Typical examples of chelating agents used in the present invention are as follows.

l-Hydroxyethylidene-1,1'-diphosphonic acid.

Sodium tripolyphosphate. Ethylenediaminetetraacetic acid. Nitrilotriacetic acid. Diethylenetriaminepentaacetic acid. Diglobanolamine tetraacetic acid. Propylenediaminetetraacetic acid. Cyclohexanediaminetetraacetic acid.

Glycol ether diamine tetraacetic acid. Nitrilo-N
, N,N-trimethylenephosphonic acid. Further, the following chelating agents can also be effectively used in the present invention.

Citric acid, tartaric acid, lactic acid, malic acid, ethylenediaminetetramethylenephosphonic acid, l,2 cyclohexanediaminetetraacetic acid, δ-carboxyanilinodimethylenephosphonic acid, propylaminodimethylenephosphonic acid, 4- (N-pyrrolidino)butylamine-N,N-bis(methylenephosphonic acid Li, 3-propanediaminetetramethylenephosphonic acid, 1,6-hexylamine:naminetetramethylenephosphonic acid, 0-acetamidobenzylaminodimethylenephosphonic acid, 10- ) luidine dimethylene phosphonic acid, 2-bilidyl amino dimethylene phosphonic acid, l-hydroxy-2-phenylethylidene-1, l'-diphosphonic acid, iminodiacetic acid, dihydrotetraxyethylglycine, ethyl ether diamine tetraacetic acid, Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diamino-2-propatoltetraacetic acid, triethylenetetraminepentaacetic acid, hydroxyethyl iminodiacetic acid, propylenediaminetetraacetic acid, N~hydroxyethylethylenediaminetriacetic acid, 1- Hydroxy-1,1-diphosphonethane-2-carboxylic acid, 1-hydroxy-1,1-diphosphonepropane-3-carboxylic acid, 1-hydroxy-1
, 1-diphosphonepropane-3-carboxylic acid, 1-hydroxy-1,1-dipospor.

Lopan-2゜3-dicarboxylic acid, ■, -hydroxy-1
．． i-diphosphonopropane-2-carphonic acid, l-hydroxy-1,1,2-)liphospono-2-methylpropane-3-carboxylic acid potassium salt, l-hydroxy-1-
Phosphonoethane-1-carboxylic acid, 1-hydroxy-1
-phosphonoethane-1,2-dicarboxylic acid, 1-hydroxy-1,2-diphosphonoethane-1-carboxylic acid, 1
-Hydroxy-1-phosphonopropane-1-carboxylic acid, l-hydroxy-1-phosphonopropane-1,2゜3
-tricarboxylic acid, l,2-dihydroxy-1-phosphonoethane-1-carbo:ylRli-human tetraxyl-
Phosphonopropane-1,3-dicarboxylic acid potassium salt,
1-Hydroxy-1-phosphono-2-ri o o, :T-
E7-1-carboxylic acid sodium salt, 1,2-dihydroxyl 1,2-diphosphonoethane-1,2-dicarboxylic acid, 1-hydroxy-1゜2.3-)IJphosphonopropane-1-carboxylic acid, l-hydroxy-1-phosphonopentane-1-carboxylic acid, l-hydroxy-1-phosphono-2-methylpropane-1-carboxylic acid, 1.1-
Diphosphonethane-2-carboxylic acid potassium salt, 2゜2
-diphosphonopropane-1-carboxylic acid, t-phosphonoethane-2-carboxylic acid, 1-hydroxy-1-phosphonoethane-2-carboxylic acid, 2-phosphono-pentane-
2,5-dicarboxylic acid, 2-methyl-1-phosphonobutane-1,4-dicarboxylic acid, 2-methyl-4-phosphonobutane-1°4-dicarboxylic acid, 1-phosphonopentane-1°4-dicarboxylic acid, 2-Methyl-4-phosphonopentane-1,4-dicarboxylic acid, 3-methyl-2-phosphonopentane-2,5-dicarboxylic acid, 2゜2-dimethyl-4-phosphonobutane-1,4-dicarboxylic acid ,2
．． 2-dimethyl-4-phosphonopentane-1,4-dicarboxylic acid, 3. -3-dimethyl-5-phosphonohexane-2,5-dicarboxylic acid, 2-phosphonobutane-1,4
-dicarboxylic acid potassium salt, 3-phosphonopentane-2
, S-dicarboxylic acid, 2-methyl-2-phosphono-butane-1,4-dicarboxylic acid, 2-methyl-3-phosphonobutane-1,4-dicarboxylic acid, 2-phosphonopentane-1,4-dicarboxylic acid, 2-Methyl-2-phosphonopentane-1,4-dicarboxylic acid, 2,3-dimethyl-2-
Phosphonobutane-1,4-dicarboxylic acid, 3-phosphonohexane-2,5-dicarboxylic acid, 2,4-dimethyl-
4-phosphonopentane-2,5-dicarboxylic acid, 2,4
-Dimethyl-4-phosphonohexane-2,5-dicarboxylic acid potassium salt, 2-methyl-4-phosphonobencune-
2,4-dicarboxylic acid, 2-phosphonopropane-2,3
-dicarboxylic acid, 3,3-diphosphobentane-1,5
-dicarboxylic acid, 2,2-diphosphonpropane-1,3
-dicarboxylic acid, 1,2-diphosphonethane-1,2-
Dicarboxylic acid, 1,2-diphosphonpropane-1,2-
dicarboxylic acid, 1,2-diphosphono-3-hydroxypropane-1,2-dicarboxylic acid, 1,2-diphosphonopropane-1,2,3-tricarboxylic acid potassium salt, 1,
2.3-triphosphonopropane-1゜2-dicarboxylic acid, 1,2.3-1-liphosphonopropane-1,2,3-
) dicarboxylic acid, 2,3-diphosphonebutane-2,3-
Dicarboxylic acid sodium salt, 2,3-diphosphone-1,
4-dihydroxybutane-2,3-dicarboxylic acid potassium salt, 1,2-diphosphonebutane-1,2-dicarboxylic acid, 1,2-diphosphonebutane-1,2,4-1licarboxylic acid, 1.2 -diphosphonobutane-1゜2.3-)dicarboxylic acid, 2.3-diphosphonobutane-1,2,3,
4-Tetracarboxylic acid, 1゜2-diphosphobentane-
1,2-dicarboxylic acid lithium salt, l,2-diphosphone-1,3-dihydroxypropane-1,2-dicarboxylic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid 1-phosphonobutane-2,3 , 4-tricarphonic acid,
1. ■-diphosphonopropane-2,3-dicarboxylic acid,
2-phosphonobutane-2,3,4-)dicarboxylic acid, 2
．． 2-diphosphonobutane-3゜4-dicarboxylic acid, 2-
Phosphonobutane-1,2,-4-tricarboxylic acid, nitrilodi(methylenephosphono)methylenecarboxylic acid, nitrilomethylenephosphonodi(methylenecarboxylic acid), propylamine-N-methylenephosphono-N-methylenecarboxylic acid, ethylenediamine-N , N'-di(methylenephosphono)-N,N'-di(methylenecarboxylic acid), 1.
2-Cyclohexanediamine-N,N'-dimethylenephosphono-N,N'-di(methylenecarboxylic acid), 1.3
-diaminopropan-2-ol-N,N'-dimethylenephosphono-N,N'-di(methylenecarboxylic acid),glycol ether diamine-N,N'-dimethylenephosphono-N,N'-di (methylene carboxylic acid).

However, the case where the washing bath of the present invention contains the chelating agent represented by the general formula [n) in combination with the compound represented by the general formula CI) is excluded.

General formula [1] General formula [In the ID constraint, RI is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, halogenated alkyl group, arylalkyl group, -RH-ORI3, -C0NHR14, bird, R,
, R2H, is a hydrogen atom, a halogen atom, a hydroxy group,
Alkyl group, amino group, nitro group, RI! represents an alkylene group, and RIsR+4 both represent a hydrogen atom and an alkyl group. R6 is a hydrogen atom, hydroxy group, amino group, "I
is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, R8H, R
IoRII and both represent a hydrogen atom, a carboxy group, and a hydroxyl group.

The chelating agents used in the present invention are each 0.0. It is preferable to use it in the range of O1 to 50p,
More preferably, good results are obtained when adding 0.05 to 20 g.

Generally, the concentration of thiosulfate in the washing water is l! Hit 0.
Sulfides are particularly likely to be generated when the concentration is in the range of 01 to 109, and less likely to occur at concentrations outside of this range, but even if they are generated, the amount generated is so small that it does not pose a problem. When using the chelating agent according to the present invention, a particularly large effect can be obtained by allowing it to be present in a treatment tank in which the concentration of thiosulfate is within the above concentration range. However, even if it is present in the processing tank at other concentrations, it will not affect the photographic performance, so any method of addition can be used.

When carrying out the processing method of the present invention using an automatic processor,
Because the residence time of the processing liquid in the processing tank is considerably longer than in the past, each processing tank is equipped with a temperature control device, agitation device (e.g., circulating air burst, nitrogen gas burst), filter, etc. It is preferable to install it in the same way as the processing liquid tank.

When the method of supplying the processing liquid in the process according to the present invention is a multi-tank countercurrent system, it is preferable that the treatment liquid is supplied to the rear bath and overflowed from the front bath. In addition, the compound according to the present invention can be added to the treatment tank as a concentrated liquid, or the compound according to the present invention and other additives may be added to the treatment liquid supplied to the treatment tank, and then mixed with the supplied liquid. There are various methods, such as adding it to a pre-processing bath, or making it present in the processing bath by adding it to the photosensitive material to be processed, and it may be added by any h5 addition method.

The chelating agent used in the present invention contains water and alcohol in order to make it easier to handle as a liquid.

Glycols, surfactants, calcium chloride, magnesium sulfate, sodium nitrate, and potassium hydroxide and sodium hydroxide for pH adjustment.

It is preferable to mix sulfuric acid, potassium carbonate, borate, phosphate 1, etc. and handle it as a stable liquid.

In order to improve the water washing efficiency1, the treatment bath of the present invention appropriately contains sulfites, organic acid salts, such as acetic acid, succinic acid, silicic acid, benzoic acid, or a fluorescent whitening agent to improve whiteness. I can do it.

The pH of the treatment solution of the present invention is not particularly critical. However, it is preferred to use a range from 6 to 2 to 9. pHt3.5-6
．． Particularly good results can be obtained when used within the range of 0.

In the treatment method of the present invention, there is no problem in using ordinary tap water with respect to the water quality 1R used for the treatment liquid, but it is preferable to use water that has been sterilized with a halogen or ultraviolet germicidal lamp. Furthermore, sterilization can be carried out by providing a sterilizing device using a halogen or ultraviolet sterilizing lamp in the processing tank.

Silver can be recovered from the process using uninvented methods such as overflow of the treatment solution or directly from the treatment tank, electrolytic method, metal replacement method, adsorption method using ion exchange resin, precipitation method using chemicals, etc. You may apply all of them. It is also possible to collect it by mixing it with stagnation liquid, bleach tail liquid, etc. In addition, in the treatment method of the present invention, the amount of washing water waste liquid is significantly reduced compared to the conventional method, so combustion methods and evaporation to dryness methods, which have not been used much in the past, are used as waste liquid treatment methods. It has become possible to use it for practical purposes as a total complete pollution system. In this case, developer.

There is no problem in treating it by mixing it with waste liquids such as foot dressing solution, bleach solution, bleach-fix solution, etc.

The processing method of the present invention can be applied to color paper, black and white paper,
Reversal color paper, color positive film, color negative film, black and white negative film, color reversal film, M
Film, X-ray film, microfilm on white skin! %3 can be used for processing any silver halide photographic material such as copying film, direct positive film, printing film, gravure film, etc.

<Effect of the invention> Next, we will summarize the effects of the treatment method of the present invention.

(1) Prevents precipitation caused by decomposition of thiosulfuric acid in the washing tank.

(2) Enables a significant reduction in flushing water.

(3) Preventing color image deterioration.

The present invention will now be described in detail with reference to Examples.

(Example 1) The following layers were sequentially coated on polyethylene coated paper from the support side to prepare a silver halide color photographic material.

The polyethylene coated paper was made by adding 6.8% by weight of anatase-type titanium oxide to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 100,000° and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2.0001 and a density of 0.80. Weight 170I by extrusion coating method!
A coating layer with a thickness of 0.035 m was formed on the surface of a high-quality paper with a thickness of 0.04 mm. After pretreatment by corona discharge, each layer was applied sequentially.

1st layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 95 mol% silver bromide. 2,5-di-t-butylhydroquinone and 2,5-di-t-butylhydroquinone, which were sensitized using 2,5 x 10-4 moles of sensitizing dye having the following structure (using all isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalade. Yellow coupler α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triacylysyl)]-]α-bivalyl-2-chloro5-r
-(2,4-di-t-amylphenoxy)butyramide]acetanilide per mole of silver halide 2 X 1
It contains 0.1 mole of silver and is coated in a silver amount of 350 to 1.0 mol.

2nd layer di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate 3oo my/m, 2-(2'-hydroxy-3',5',-di-t
-butylphenyl)benzotriazole, 2-(2'-
h)"oxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3t-t-phthyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy -3', gi-ji-
A gelatin layer containing 200 m9/me of a mixture of tert-butylphenyl)-5-chlorobenzotriazole is coated in such a manner that the gelatin layer is coated with gelatin z, ooo.

Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide.The emulsion contains 450F gelatin per mol of silver halide. Sensitized using 2,5 x IF' moles of a sensitizing dye with the following structure per mole of silver halide containing dibutyl phthalade and tricresyl phosphate 2:IJ:, 7
2,5-di-t-butylhydroquinone and magenta coupler 1-(2°4,6-
) Lichlorophenyl)-3-(2-chloro-5-occudecenylsuccinimidoanilino)-5-pyrazolone gold halide @1 mole contains 1.5xio-' mole, silver amount 400 mg/ 2.3.4-trimethyl-6-lauryloxy-7-1-octylchroman was applied as an oxidation preventive agent in an amount of 0.5 mole per mole of coupler. include.

Fourth layer di-t-octylhydroquinone 30'Qk dissolved and dispersed in di-glyphthalate and 2-(2'-hydroxy-3',5'-di-t-
Benzotriazole, 2-(2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydroxy-g-t-benzotriazole)
-methylphenyl)-5-10 rubensotriazole,
A mixture of 2-(2'-hydroxy-3',5'-t-butylphenyl)-5-chloro-benzotriazole (2
: 1.5 : 1.5 : 2) gelatin layer containing soo gelatin 2. Ooomr I'm drooling from the application.

Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 500.9' gelatin per mol of silver bromide, 2,5-di-t-butylhydroquinone and the cyan coupler 2,4-sensitized using 2.5XIO → moles of a sensitizing dye of the following structure per mole of silver, dissolved and dispersed in dibutyl 7-talate. dichloro-3
-Methyl-6-[r(2,4-cyamylphenoxy)butyramide]phenol per mole of silver halide 3
．． It contains 5 x 10-' moles and is coated to give a silver content of 270 to I.

The 611th Seratin layer is coated with gelatin + 1.000 thick.

The silver halide emulsions used in each light-sensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and sodium thiosulfate pentahydrate was added to each emulsion. Chemically sensitized using 4-hydroxy-6 as a stabilizer
-methyl-1,3,3a, 7-chitrazaindene,
Contains bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.

The color paper prepared by the above method was subjected to decomposition step exposure using a photosensitive needle using blue, green, and red filters, and the following treatments were performed.

The treatment steps and composition of the treatment bath at this time are as follows.

Standard processing step 1 Color development 33℃ 3 minutes 30 seconds 2 Bleach fixing 33℃ 1 minute 30 seconds 3 Washing with water
30~35℃ 3 minutes 4 drying 75~
The composition of the treatment solution at 80° C. for about 2 minutes is as follows.

[Color developer]

Benzyl alcohol 15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 p Potassium bromide
0.7.9 Sodium chloride
02I! potassium carbonate
30.09 Hydroxylamine sulfate 3.09 Polyphosphoric acid (TPPS) 2.5g3
-Methyl-4amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate
5,5y fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative 1.0 g Potassium hydroxide 2.09 Add water to make 11.

[Bleaching foot solution]

Ethylenediaminetetraacetic acid ferrous ammonium dihydrate 60 pEthylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution 1) 100rfLl Ammonium sulfite (4
(0% solution) Adjust the pH to 7.10 with 27.5 m potassium carbonate or glacial acetic acid. Add water to bring the total volume to 1 liter.

[Treatment bath (1)] Tap water [Treatment bath (2)] 1-hydroxyethylidene-1,1'-diphosphonic acid
After adjusting the pH'i to 5.0 with 1 g potassium hydroxide, water was added to make it IA'.

[Treatment bath (3)] 1.2-benziisoiazolin-3-one O15:y
Tripoly-su+lium phosphate 1. After adjusting the pH to 5.0 with O1 sulfuric acid, water was added to make up to 1 liter.

[Treatment bath (4)] 1.2-benzisothiazolin-3-one 0.5 g ethylenediaminetetraacetic acid i-og After adjusting the pH to 5.0 with potassium hydroxide, water was added to make the solution to 11.

Treatment bath (5)] 1.2-benzisothiazolin-3-one 0.5 g Nitrilotriacetic acid 1.0. After adjusting the pH to 5.0 with lit potassium hydroxide, add water to make it to ix.

[Treatment bath (6)] 1.2-benzisothiazolin-3-one 0.551 diethylenetriaminepentaacetic acid 1.0 & potassium hydroxide to adjust I) H'fil" to 5.0, then add water to 11
Finish it.

[Treatment bath (7)] 1.2-benzisothianlin-3-one 0.5 g dibrova, nolaminetetraacetic acid 1.0 g
After adjusting the pH to 5.0 with potassium hydroxide, the pH was adjusted to 11 by adding water.

[Treatment bath (8)] 1.2-benzisothiazolin-3-one 0.5 g Propylene diamine tetraacetic acid 1.0 g After adjusting the pH to 50 with potassium hydroxide, add water to make up to 1 liter.

[Treatment bath (9)] 1.2-benzisothiazolin-3-one 0.5g cyclohexanediaminetetraacetic acid 1. After adjusting the pH' (r-5.0) with OFJ potassium hydroxide, add water to adjust the pH to 11.

[Treatment bath α0] 1.2-benzothiacylyly/-3-one 0.5,
! i+Glycol ether diamine tetraacetic acid 1o
After adjusting the pHKl to 5.0 with potassium hydroxide, add water to make a final pH of 11.

[Treatment bath (lυ)]

1.2-benzisothiazolin-3-one 0.5p=
) I) 1: I -N, N, N-trimethylenephosphonic acid 1.0 g After adjusting the pH to 5.0 with potassium hydroxide, add water to make up to 1 liter.

All the samples obtained by treatment with the above treatment baths (1) to Qll and drying were left for 5 weeks at 60°C relative temperature 80% and 77°C relative temperature 2%, and the minimum blue density and maximum red density were measured. The results are shown in Table 1.

-371 Table Note) Immediately after treatment, the minimum blue density was 0.04, and the maximum red density was 2.56±0()5.

From Table 1 above, those treated with processing bath side ~Q have less occurrence of yellow stain in unexposed areas and a decrease in cyan pigment compared to those treated with comparative treatment bath (1) ~ 0υ゛. It was found that the dye image was small and had excellent stability.

Moreover, the general formula [1] or the general formula [I[) of the compound of the present invention
It was found that the desired result could not be obtained even if the compound represented by was used alone, and that the desired result could only be obtained by coexisting with the compound.

In addition, chelating agents such as citric acid, tartaric acid, lactic acid, malic acid, ethylenediaminetetramethylenephosphonic acid,
．． 2-Cyclohexanediaminetetramethylenephosphonic acid, 0-carboxyanilinodimethylenephosphonic acid, propylaminodimethylenephosphonic acid, 4-(N-pyrrolidino)butylamine-N,N-bis(methylenephosphonic acid), 1゜3-propanediamine Tetramethylenephosphonic acid, 1.6-hexanediaminetetramethylenephosphonic acid, 0-acetamidobenzylaminodimethylenephosphonic acid, o-toluidine dimethylenephosphonic acid, 2-
Pyridylaminodimethylenephosphonic acid, 1-hydroxy-2-7enylethylidene-1°1'-diphosphonic acid,
Iminodiacetic acid, dihydroxyethylglycine, ethyl ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1.3-
diamino-2glopanoltetraacetic acid, triethylenetetraminepentaacetic acid, hydroxyethyliminodiacetic acid,
Propylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, 1-hydroxy-1,1-
Diphosphone-ethane-2-carboxylic acid, l-hydroxy-1,1-diphosphonobroban-3-carboxylic acid, l
-Hydroxy-1,1-diphosphone-propane-2,3
-dicarboxylic acid, l-hydroxy-1,1-dibosphonopropane-2-carboxylic acid, l-hydroxy-1゜1.
2-) Liphosphono 2-methylpropane-3-carboxylic acid potassium salt, 1-hydroxy-1-phosphonoethane-
1-carboxylic acid, l-hydroxy-1-phosphonoethane-1,2-dicarboxylic acid, 1-hydroxy-1,2-diphosphonoethane-1-carboxylic acid, 1-hydroxy-1
-phosphonopropane-1-carboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-)dicarboxylic acid, 1,2-dihydroxy-1-phosphonoethane-1-carboxylic acid, 1-hydroxy-1 -phosphonopropane-1
,3-dicarboxylic acid potassium [,1-hydroxy-1-
Phosphono-2-chloroethane-1-carboxylic acid sodium salt, 1,2-dihydroxy-1,2-diphosphonoethane-1,2-dicarboxylic acid, 1-hydroxy-1,2,
3-1-liphosphonopropane-1-carboxylic acid, l-hydroxy-1-phosphonopentane-1-carboxylic acid, 1
-Hydroxy-1-phosphono-2-methylpropane-1
-carboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid potassium salt, 2,2-diphosphonopropane-1-carboxylic acid, 1-phosphonoethane-2-carboxylic acid, 1-
Hydroxy-1-phosphonoethane-2-carboxylic acid, 2
-phosphonopentane-2,5-dicarboxylic acid, 2-methyl-1=phosphonobutane-1,4-dicarboxylic acid, 2-
Methyl-4-phosphonobutane-1,4-dicarboxylic acid,
■-phosphonopentane-1,4-dicarboxylic acid, 2-methyl-4-phosphonopentane-1,4-dicarboxylic acid,
3-Methyl-2-phosphonopentane-2,5-dicarboxylic acid, 2,2-dimethyl-4-phosphonobutane-1,4
-dicarboxylic acid, 2,2-dimethyl-4-phosphonopentane-1゜4-dicarboxylic acid, 3,3-dimethyl-5-
Phosphonohexane-2,5-dicarboxylic acid, 2-voshoptane-1,4-dicarboxylic acid potassium salt, 3-phosphonopentane-2,5-dicarboxylic acid, 2-methyl-2
-phosphonobutane-1,4-dicarboxylic acid, 2-methyl-3-phosphonobutane-1,4-dicarboxylic acid, 2-phosphonopentane-1,4-dicarboxylic acid, 2-methyl-
2-phosphonopentane-1,4-dicarboxylic acid, 2.3
-dimethyl-2-phosphonobutane-1,4-dicarboxylic acid, 3-phosphonohexane-2,5-dicarboxylic acid, 2
．． 4-dimethyl-4-phosphonopentane-2,5-dicarboxylic acid, 2,4-dimethyl-4-phosphonohexane-
2,5-dicarboxylic acid potassium salt, 2-methyl-4-phosphonopentane-2゜4-dicarboxylic acid, 2-phosphonopropane-2゜3-dicarboxylic acid, 3,3-diphosphobentane-1,5 -dicarboxylic acid, 2,2-diphosphonepropane-1,3-dicarboxylic acid, 712.1.2-diphosphonethane-1,2-dicarboxylic acid, 1,2-diphosphonepropane-1,2-dicarboxylic acid, 1゜2-diphosphone-3-human □roxypropane-112-dicarboxylic acid, 1.2-diaminopropane-1,2,3-)dicarboxylic acid potassium salt, 1゜2.3-triphosphonopropane-1,2- dicarboxylic acid, 1,2.3-triphosphonopropane-1°2.3-) dicarboxylic acid, 2.3-diphosphonobutane-2,3-dicarboxylic acid sodium salt, 2.
3-diphosphone-1,4-dihydroxybutane-2゜3
-Dicarboxylic acid potassium salt, 1,2-diphosphonobutane-1,2-dicarboxylic acid, 1,2-diphosphonobutane-1,2,4-)dicarboxylic acid, l.

2-diphosphonobutane-1,2,3-)licarbo-4-tetracarboxylic acid, 1,2-diphosphonobutane-1,2
-Dicarboxylic acid lithium salt, 1,2-diphosphone-1,
3-dihydroxypropane-1,2-dicarboxylic acid, 1
-phosphonopropane-1,2,3-tricarvone rRζ
1-phosphonobutane-2,3,4-tricarboxylic acid,
1.1-diphosphonpropane-2,3-dicarbo/acid,
2-Phosulfonogutan-2.3.41 Ricarboxylic acid, 2
゜2-Diphosphonbutane-3,4-dicarboxylic acid, 2-
Phosphonobutane-1,2,4-11carboxylic acid, nitrilodi(methylenephosphono)methylenecarboxylic acid, nitrilomethylenephosphonodi(methylenecarboxylic acid), propylamine-N-methylenephosphono-N-N methylenecarboxylic acid, ethylenediamine- N,N'-di(methylenephosphono)-N.

N'-di(methylenecarboxylic acid), 1,2-cyclohexanediamine-N, N'-dimethylenephosphono-N, N
'-di(methylenecarboxylic acid), 1,3-diaminopropan-2-ol-N, N'-dimethylenephosphono-N
, N'-di(methylenecarboxylic acid), glycol ether diamine-N, N'-dimethylenephosphono-N, M-
Di(methylenecarboxylic acid), % each (2)
1-Hydroxylene 1,1'-dipho? When similar tests were performed in place of fonic acid, they showed the same performance as the rectangular sleeping bath (21~(]υ).

Claims (1)

[Claims] 1. A method for developing exposed silver halide photographic materials, which comprises processing with an aqueous solution containing a chelating agent following a processing step containing a thiosulfate.