JPS61117541A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance bleachability and fixability of a color photographic material high in sensitivity, and to enable processing at high speed with a decreased bath by processing said material with a bleach-fixing soln. contg. a specified org. acid ferric complex salt and a di- or mono-carboxylic acid. CONSTITUTION:The silver halide color photographic sensitive material is imagewise exposed and developed, and then, processed with a bleach-fixing soln. contg. at least one of ferric complex salts of org. acids, as a bleaching agent, having a free acid mol.wt. of >=290, preferably, >=350, and di- or mono- carboxylic acid, preferably, aminodi- or aminomono-carboxylic acid in an amt. of >=2mol% of the ferric complex salt. Such a bleach-fixing processing permits fixability to be enhanced and superior desilvering effect to be obtained and high speed and stability of processing to be secured.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic materials, and more particularly to a method for processing silver halide color photographic materials improved in a bleach-fixing step. It is.

[Prior art]

Generally, in order to obtain a color image by processing a silver halide color photographic material (hereinafter referred to as a color sensitive material) that has been imagewise exposed, after a color development step, the generated metallic silver is treated with a bleaching ability. A step of treating with a liquid is provided.

A whitening solution and a bleach-fixing solution are known as processing solutions having a whitening ability. When a bleaching solution is used, a step of fixing the halogenated dye with a fixing agent is usually added after the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step.

Processing solutions with bleaching ability for processing color sensitive materials include:
Inorganic oxidizing agents such as blood salts and dichromates are widely used as oxidizing agents for bleaching image silver.

However, the treatment solution containing an inorganic oxidizing agent and having a marking ability has problems in terms of toxicity and corrosion of treatment machine parts, and is not completely satisfactory for practical use.

On the other hand, organic acids such as aminopolycarboxylic acid metal complex salts are used as oxidizing agents to meet the requirements of speeding up and simplifying treatment, and enabling recycling of waste liquids, with fewer pollution problems. In recent years, treatment solutions have come to be used.

In addition, thiosulfates, thiocyanates, thioureas, thioethers, highly concentrated odorous substances, iodides, etc. are known as fixing agents, but they are relatively stable and are excellent as fixing agents. Thiosulfates are widely used.

However, in the bleach-fixing process, various problems have arisen due to the coexistence of bleaching agents, which are oxidizing agents, and fixing agents, sulfites, etc., which are reducing agents. In particular, it has been difficult to process high-sensitivity color photosensitive materials with a bleach-fixing solution because both bleaching and fixing properties are insufficient, especially for high-sensitivity color photosensitive materials with a large amount of coated silver, such as those containing silver iodide. .

For example, if an oxidizing agent is added to increase the redox potential of the solution in order to increase the bleaching speed, the fixing component will be oxidized and easily sulfurized, and in severe cases, silver sulfide will be generated, which could lead to an irreversible accident. do not have.

Furthermore, if the concentration of the fixing agent is increased too much in an attempt to increase the fixing speed, the fixing speed will instead decrease, becoming the rate-limiting step in the bleach-fixing reaction and deteriorating the bleach-fixing speed.

For this reason, it is impossible to use red blood salts, persulfates, bromates, etc., which have high oxidizing power, and it is necessary to use organic acid ferric complex salts, etc., which have weak oxidizing power.

In other words, it can be seen that the bleach-fix solution has the drawbacks of low stability and insufficient bleaching and fixing performance in terms of speed, so it has not been put to practical use as a treatment for high-sensitivity photosensitive materials. .

In general, the desilvering rate of a bleach-fix solution is high when the pH is low (,
It is known that as PR increases, it decreases.

Normally, color development is directly followed by bleach-fixing, and a high-pH □ color developing solution is brought in, which tends to increase the pH of the bleach-fix solution and lower the bleach-fix reactivity. Furthermore, since the pH in the film is high, there is also the drawback that the initial bleach-fixing speed is slow. Particularly in recent years, the replenishment method for bleach-fixing processing has become so-called a non-regeneration method, which simply replenishes the fixing agent necessary to complex the missing components and silver ions eluted in the bleach-fix solution when processing photosensitive materials. Since it has been adopted, the amount of replenishment for bleach-fixing is extremely small, resulting in the problem of instability due to the significant influence of the color developer brought in.

Furthermore, in a method where the amount of replenishment is small, the amount of silver ion concentration accumulated in the bleach-fix solution increases (this not only reduces the bleaching constant N rate but also increases the amount of silver ion concentration that is accumulated in the bleach-fix solution due to washing with water and the stabilizing solution due to the photosensitive material being carried out to the next process). Losses due to leakage are increasing and causing extremely large economic losses.

In order to solve these shortcomings, the
No. 46-280, Tokuko Sho, 16-5
As described in Japanese Patent Publication No. 56, JP-A No. 49-5630, etc., a bleach accelerator is used in addition to a bleach-fixing solution containing mainly ethylenediaminetetraacetic acid iron tetracomplex salt as an oxidizing agent. However, it is not always possible to obtain a satisfactory bleaching promotion effect. Moreover, there are problems such as the formation of poorly soluble precipitates when silver dissolves and accumulates, making it extremely impractical. In addition, a method of using ferric salt of diethylenetriaminepentaacetic acid as a bleaching agent was disclosed by the present inventors in JP-A-59-1493.
This method has been proposed in Publication No. 58 and Publication No. 59-151154. However, although these methods achieve the desired bleaching speed and accelerate the bleach-fixing speed and intensity as a whole, the fixing speed is insufficient and only traces of silver halide remain when processing high-sensitivity materials containing high iodine. The inventors' studies have revealed that so-called desilvering defects are observed.

(Object of the Invention) Accordingly, an object of the present invention is to provide a processing step that improves the bleaching and fixing properties of a high-sensitivity color photosensitive material and is more rapid than processing at a lower temperature.

[Structure of the invention]

As a result of extensive studies, the present inventors have determined that the molecular weight of the free acid is It has been found that this can be achieved by treatment with a bleach-fixing solution containing at least one organic acid ferric complex salt having a ferric acid complex salt having a ferric acid of 290 or more and at least one dicarboxylic acid and/or monocarboxylic acid.

More preferably, an aminopolycarboxylic acid ferric complex salt whose free acid has a molecular weight of 350 or more is used as the bleaching agent. Further, it is preferable that the dicarboxylic acid and/or monocarboxylic acid is an amino dicarboxylic acid and/or an aminomonocarboxylic acid, and the content thereof is 2 mol % or more based on the ferric aminopolycarboxylic acid complex salt.

The present invention will be explained in detail below.

The present inventors have investigated processing a color photosensitive material containing silver iodide with a single-bath bleach-fix solution, which is a simple processing step. In addition, as a result of repeated studies on rapid processing and on processing methods that do not cause the various troubles mentioned above, we have found that, in particular, when bleaching agents made of ferric aminopolycarboxylic acid complex salts are used in high concentrations, It was found that the fixing reaction was significantly suppressed as the concentration increased, and it was also found that the delay in the fixing reaction was caused by a delay in the diffusion of the fixing agent. It was found that the delay in the fixing reaction forms a rate-limiting step in the bleach-fixing reaction, and in particular, it significantly suppresses the initial reaction and forms an induction period. It has been found that the delay in fixing reaction is particularly significant in the processing of color sensitive materials containing silver iodide.

Further, it was found that, as a matter of course, the delay in the fixing reaction was significant as the amount of silver increased. This phenomenon occurs especially when the organic acid ferric complex salt is 6011/1 or more, especially when 80 g
It was also found that it was significant at /1 or higher. It has also been found that this suppression phenomenon increases as the molecular weight of the free acid constituting the organic acid ferric complex salt increases, and becomes significantly larger when the molecular weight exceeds 290. This phenomenon correlates with the degree of swelling during bleach-fixing, and the larger the molecular weight, the smaller the degree of swelling during the process.

Based on this phenomenon, the present inventors proposed that, as an effective means for preventing suppression of the fixing reaction, the bleach-fixing solution should contain at least one kind selected from dicarboxylic acids and/or monocarboxylic acids and a free acid having a molecular weight of 290 or more. We proposed treatment with a treatment solution containing at least one type of organic acid ferric complex salt, but if the organic acid ferric complex salt has a free acid molecular weight of 290 or less, the bleaching performance would deteriorate and a single-bath solution was requested. I can't answer that at all. Furthermore, when a polycarboxylic acid other than a dicarboxylic acid or a monocarboxylic acid is used, it is not possible to effectively prevent the fixation reaction, and as a result of various studies by the present inventors, it is not possible to effectively prevent the fixing reaction, and a trace level of unbuttoning failure occurs. , which led to the completion of the present invention.

The bleaching agent used in the bleach-fix solution of the present invention is an organic acid ferric complex salt whose free acid has a molecular weight of 290 or more.

More preferred is an aminopolycarboxylic acid ferric complex salt having a free acid molecular weight of 350 or more.

Specific representative examples of the aminopolycarboxylic acid forming the ferric aminopolycarboxylic acid complex salt of the present invention are listed below, but the aminopolycarboxylic acid of the present invention is not limited to these specific representative examples.

(11 ethylenediaminetetraacetic acid (BDTA) (MW=2
92.25) (2) Diethylenetriaminepentaacetic acid (DTPA) (
Mv=393.27) +3) Diethylenetriaminepentamethylenephosphonic acid (DTPP) (Mw=573.12) (4) Cyclohexanediaminetetraacetic acid (CyDT&
) (My = 364.35) (51 cyclohexanediamine tetramethylene phosphonic acid (
CyDTP) (Mw=508.23)(6))
Liethylenetetraminehexaacetic acid (TTHA) (Mw =
494.45 )- (7) Triethylenetetramine hexamethylenephosphonic acid (
[” THP ) (Mw= 710.27) (8)
Glycol ether diamine tetraacetic acid (GEDTA)
(Mw = 380.35) (9) Glycol ether diamine tetramethylene phosphonic acid (GEDTP) (
Mw=524.23) flcI 1,2-diaminopropanetetraacetic acid (M-EDTA) (Mw-306,2
7) (1111,2-diaminopropane tetramethylenephosphonic acid (M-EDTP) (Mw=450.15)
ft, 1,3-diaminopropan-2-oltetraacetic acid (DPTA-OH) (Mw=322.27) (r→
1.3-diaminopropan-2-ol tetramethylenephosphonic acid (DPTP-OH) (Mw=466.15) (1
4 ethylenediamine diorthohydroxyphenylacetic acid (
EDDHA) (Mw=360.37)fld
Ethylenediaminediorthohydroxyphenylmethylenephosphonic acid (Mw=432.31) ftd Ethylenediaminetetramethylenephosphonic acid (Mw=436
．． 13) The organic acid ferric complex salt of the present invention may contain any one of these.
wi can be selected and used, and two or more types can be used in combination as necessary.

Among the organic acids forming the organic acid ferric complex salt of the present invention, the following are particularly preferable in terms of fixability, rapidity, stability, etc.

(I) Diethylenetriaminepentaacetic acid (n) Cyclohexanediaminetetraacetic acid (■) Triethylenetetraminehexaacetic acid The ferric complex salts of organic acids according to the present invention include free acids (hydrogen salts), sodium salts, potassium salts, and lithium salts. It is used as an alkali metal salt such as, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt, but preferably a potassium salt, a sodium salt, and an ammonium salt are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination.

The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but generally it is used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. Can be used. For example, it is preferably used in an amount of 0.105 to 0.6 mol. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The dicarboxylic acid and/or monocarboxylic acid used in the present invention is preferably amino dicarboxylic acid and/or aminomonocarboxylic acid, and is used in an amount of 2 mol % or more based on the ferric salt of the organic acid. The range preferably used is 2 to 200 mol%. The aminodicarboxylic acids and aminomonocarboxylic acids include the following specific representative examples, but the dicarboxylic acids and monocarboxylic acids of the present invention are not limited to these specific representative examples.

ta+ dihydroxyethylglycine (DHEG)l
b) Hydroxyethyliminodiacetic acid (T(IDA)
(c) Iminoniacetic acid (IDA) (al Methyliminodiacetic acid (Me-IDA) (,1
Ethylenediaminediacetic acid (EDDA) (f) Oxalic acid (p) Tartaric acid (g) Malonic acid
(ql Benzoic acid (h) Succinic acid M
Glycolic acid (i) Glutaric acid (lI)
Glycidic acid (J) Maleic acid (1) Alanine (k) Phthalic acid (u) Oxaluric acid (11Adipic acid (vl) Naphthoic acid (m
) Propionic acid (W) Stearic acid (n)
Capric acid (x) Lactic acid (,) Butyric acid The aminodicarboxylic acid and/or aminomonocarboxylic acid according to the present invention can be a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or It is used as an ammonium salt or a water-soluble amine salt such as a triethanolamine salt, and preferably potassium salt, sodium salt and ammonium salt are used. At least one of these may be used, but two or more may also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver in the photosensitive material to be processed, the composition of the halogenated steel, etc.;
It can be used in an amount of 1 mol or more, preferably 0.05 to 0.6 mol. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The fixing components used in the present invention include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate, or thioureas, thioethers, and high concentrations. bromide, iodide, etc., but it is preferable to use thiosulfate as the fixing agent. These fixing agents can be used with 51,171 or higher buds within the soluble range.

Other substances added to the bleach-fix solution include halogen compounds such as ammonium A, sodium bromide, ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, and metabisulfite. Sulfites such as potassium sulfite and sodium metabisulfite, boric acid, borax, hydroxide)
IIium, potassium hydroxide, sodium carbonate, carbonic power 1
It can contain one or more pH buffers consisting of various salts such as 1 um, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Furthermore, various fluorescent brighteners, antifoaming agents, or surfactants can be contained.

When separately replenishing a bleach-fixing replenisher to a bleach-fixing agent (bath), the constituent liquid of the present invention may contain thiosulfate, thiocyanate, sulfite, etc., or may be separated and refilled. good.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired.
or a suitable oxidizing agent such as hydrogen peroxide, bromate,
Persulfates and the like may be added as appropriate.

The bleach-fix solution of the present invention can be used at a pH of 0.2 to 9.5, preferably 4.0 or higher, more preferably 5.0 or higher, and most preferably 5.0 to 9.0. 5 or less. The treatment temperature is preferably 80° C. or lower, and more preferably 55° C. or lower to suppress evaporation.

To further explain the present invention in detail, the color developing agent used in the present invention is preferably a halapenylenediamine non-color developing agent having at least one water-soluble group (R aqueous group) on an amine group, and specific compounds include: Examples include the following compounds, but the present invention is not limited thereto.

Exemplary compounds of color developing agents; N.H.

NHt (h) C2H5(CH2CH20)2 CH3NH
t The alkaline color developing solution used in the present invention contains, in addition to a paraphenylenediamine color developing agent having at least one water-soluble amine group, various components normally added to color developing solutions, For example, phenidone and its derivatives, methonyl,... developing agents such as hydroquinone, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali-17 metal bisulfites, alkali metal thiocyanates, 7
A/, +717 Water softeners and thickeners such as metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, and surface overdevelopment prevention of trace amounts of iodides and mercapto compounds. It is also possible to optionally contain agents and the like. The P* value of this color developing solution is usually 7 or more, most commonly about 10 to about 13.

In the processing method of the present invention, a stop bath, water washing, and a processing bath having a fixing action may be used between the color development and the bleaching treatment. Further, before the color development process, processing may be performed using a processing bath having a black-and-white development or fixing effect.

Furthermore, after bleaching and fixing, a stabilization treatment may be performed without washing or substantially no washing, or a stabilization treatment may be performed after washing with water and then stabilization. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.

Silver halide emulsions that can be used in silver halide color photographic light-sensitive materials that can be treated in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, Any silver iodobromide, silver chloroiodobromide, or a mixture thereof may be used. Furthermore, as protective colloids for these silver halides, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver halide emulsion contains color couplers, stabilizers,
Common photographic additives such as sensitizers, hardeners, sensitizing dyes, and surfactants may also be included.

The processing method of the present invention can be applied to silver halide color photographic light-sensitive materials such as color bene <-, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal power rabeno (-). Can be applied.

(Examples) The present invention will be described in detail below with reference to Examples, but the embodiments of the present invention are not limited thereby.

Example (1) A multilayer color photosensitive material sample consisting of each layer having the composition shown below was prepared on a polyethylene terephthalate film support.

1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone 3rd layer: 1st red-sensitive emulsion layer Silver iodide (silver iodide = 4.0 mol%, average grain size 0.5 μm)
Monodispersed spherical particles... Silver coating amount 1. o l/Tr7'' Sensitizing dye ■...6 x 10 mol per mole of silver Sensitizing dye ■...1.5XIO per mole of silver
Morcian coupler: 0.05 per mole of silver
0 mol 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide (silver iodide = 6 mol% emulsion containing average grain size 1.0
Monodisperse spherical particles of μm... Silver coating amount 2.0 i/m sensitizing dye I.
...3.5XIO mole sensitizing dye per mole of silver■...1.0xIO mole per mole of silver
Morcian coupler...0.02 per mole of silver
0 mol 5th layer: Intermediate layer Same as 2nd layer 6th layer: 1st green-sensitive emulsion layer Silver iodobromide (Silver iodide: 3.5 mol% Average grain size 0.5 μm
(spherical monodispersed emulsion) ・・・・・・・・・Amount of silver coated 2. O1i/Go sensitizing dye I
n...3.3XlO mol per mole of silver Sensitizing dye lv...1.1X' per mole of silver
lO mole Magenta coupler 15.9 per mole of silver 7th layer: Second green-sensitive emulsion layer containing silver iodobromide (silver iodide = 3.5 mol %) Emulsion average grain size 1.
2μm monodispersed spherical particles......Silver coated t 2.09/lr? Sensitizing dye■...2.65X.lO mol per mol of silver Sensitizing dye IV...0.89X per mol of silver
IO mole magenta coupler...0.0 per mole of silver
15 mol 8th layer: Yellow filter single layer Yellow colloidal silver in gelatin aqueous solution and 2°5-di-t
- Gelatin layer containing an emulsified dispersion of octylhydroquinone Ninth layer: First blue-sensitive emulsion layer Silver iodobromide (Silver iodide = 6.0 mol% Average grain size 0.6 μm
(spherical particles) ...... Silver coating amount 2. o9/ze yellow coupler...0.25 mol per mol of silver 10th layer: 2''#Sensitive emulsion layer method embodiment # (Silver iodide = 5.0 mol% Average grain size 1 .0μm
(spherical particles) ......Silver coating amount 1.40J9/Go Yellow Cabler...0.06 mol per 1 mol of silver 11th layer: 1st retention layer Iodor Silver iodide (silver iodide: 0.5 mol%, average grain size 0.05μ)
m) ...... Silver coating amount 1.0 g 12th gelatin layer containing an emulsified dispersion of ultraviolet absorber:
In addition to the above-mentioned composition, a gelatin hardener and a surfactant were added to each layer of the gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm).

Sensitizing dye I: anhydro-s, s'-cycloloi, 3
'-di(r-sulfopropyl)-9-ethy-9ζ - ruthiacarbocyanine hydroxide pyridium salt sensitizing dye ■: Anhydro-9-ethyl-3,3'-cy (1-s/L'J'C-propy/I/)-4,5,4'
, 5'-dibenzothiacarbocyanine hydroxide.
Triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5,51-dichloro-3,37-di(r-sulfopropyl)oxacarbocyanine sodium salt sensitizing dye IV: 7:y human ct -5+ 6,5
', 6'-ftradichloro-1,1'-diethyl-3
, 3'-di(β-[β-(r-sulfopropoxy)ethoxy])ethylimidazolocarbocyanine hydroxide sodium salt.The cyan, magenta and yellow couplers are shown in the structures below.

(Cyan coupler) -ka- (Magenta coupler) (Yellow coupler) After this sample was exposed to light in a conventional manner, it was subjected to the following treatment.

Processing process Processing temperature (°C) Processing time 1 color development 37.8 3 minutes 15 sheets 2 bleach-fixing
37.8 Listed in Table 1 3 Washing - 34 2 minutes 4 Stable 30 - 34 1 minute 5 drying The following color developing solution, bleach-fixing solution and stabilizing solution were used.

[Color developer] Potassium carbonate 30 9 Sodium sulfite 2.09 Hydroxylamine sulfate m 2.2 g Potassium bromide 1.2 g Sodium diethylenetriaminepentaacetate 2.0 g Potassium hydroxide 3.4 g N-ethylene-N
-β-Hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.6g Add water to 10100O
' and adjusted to pH 10.06 with sodium hydroxide.

[Bleach-fix solution Organic acid ferric complex salt 0.31 mol Organic acid (Table (1)) 0.05 mol 2-Amino-5-mercaptothiadiazole 1.0
9 Ammonium sulfite (50% solution) lome
Ammonium thiosulfate (70% solution) 2-00ml Color developer (above) Add 100mA' water to make 1000rnt, ammonia water (28%
Solution) Adjusted to pH 7, Q 〇 Add water to 1000
Finish to ml. Ratio [Iron complex salt and dicarboxylic acid, monocarboxylic acid and the present invention Comparison comparison of the present invention Comparison of the present invention Comparison of the present invention Comparison table (1) Ax NTA: As is clear from the nitrilotriacetic acid table (1), the present invention By using an organic acid ferric complex salt and an aminodicarboxylic acid or an aminomonocarboxylic acid in combination, the time required to complete bleach-fixing is greatly shortened. Table 1 shows that when using organic acid ferric complex salts or aminopolycarboxylic acids other than those of the present invention, the bleach-fixing completion time becomes longer.
1) More noticeable.

In addition, as an organic acid ferric complex salt, M -EDTAFe (m
), TTHAFe(III), DTPPFe(III
), CyDTPFe (IIT) and TTHPFe (m
) Furthermore, Me-IDA succinic acid, malonic acid, sulfuric acid, and maleic acid were used as dicarboxylic acids, and propionic acid, glycholic acid, stearic acid, and glycidic acid were used as monocarboxylic acids in the same manner as in Example (1). The results were similar to those shown in Table f1).

Example (2) Bleach-fix solution sample N [122-28 used in Example (1)
Experiments were conducted on the bleaching properties and fixing properties of the sensitive material used in Example +11.

The floating and fixing properties were examined by simultaneously putting the photosensitive material into a bleach-fix solution, taking out samples one by one from the bleach-fix solution at 1-minute intervals, and checking the amount of remaining silver. The bleaching property was determined by removing the sample from the bleach-fixing solution at 1 minute intervals using the method described above, then fixing thoroughly and measuring the amount of silver. Fixability was determined by directly putting an unexposed light-sensitive material into a bleach-fix solution, taking it out from the bleach-fix solution at 1 minute intervals, and measuring the amount of silver.

The results are shown in Tables +2) and (3).

Table (2) Table (3) Table (2) shows that regardless of the type of aminodicarboxylic acid, aminomonocarboxylic acid, and aminopolycarboxylic acid outside the present invention, there is no significant effect on bleaching properties, but Table (3) clearly shows that This has a serious effect on fixing properties.

Particularly in the later stages of fixation, it is difficult to remove the silver even though the amount of remaining silver is small. From the above, it is clear that the use of the aminomonocarboxylic acid and aminodicarboxylic acid of the present invention greatly improves the fixing properties.

Example (3) A running experiment was conducted using the sensitive material of Example (1). Potassium bromide 0.99 hydroxyamine fA acid salt 3.19 Sodium diethylenetriaminepentaacetate 3.29
N-ethylene-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 5.4g Potassium hydroxide 2.09 Add water to make up to 11, and add P with potassium hydroxide or 20% sulfuric acid.
Adjusted to HIO, 12.

[Bleach-fixing replenisher organic acid iron(III) complex salt (listed in Table (3)) 0.4 mol-
A- Organic acid (listed in Table (3)) 0.05
Mol ammonium sulfite (50% solution) 20 Hemp 2-amino-5-mercaptothiadiazole 1.5 g
Ammonium thiosulfate (70% solution) 260ml ammonia water (28% solution) 10ml water
pH 7 with acetic acid and aqueous ammonia.
Adjusted to 0.

[Stable replenishment solution] Formalin (35% aqueous solution) 7 Add water to make 11.

The color development replenishment solution is replenished to 15 rn1 color development bath per 100d of color negative film, and the bleach-fixing replenishment solution is added to 100cr of color negative film! 8 ml of bleach-fix bath is replenished. Also, the stable replenishment liquid is color negative film 1.
Refill 10ml per 00d, water 150r per 100d
nl flowed.

The processing amount was 2017L of color negative film per day, and processing was performed until the replenishment stitches were three times the tank capacity.Example (1)
was calculated using the same method. The results are shown in Table (4).

Table (4)

Claims (1)

[Scope of Claims] 1) A method for processing a silver halide color photographic material in which the silver halide color photographic material is developed after imagewise exposure and treated with a bleach-fix solution, wherein the molecular weight of the free acid is 290.
A silver halide color photographic light-sensitive material which is processed with a bleach-fix solution containing at least one of the above organic acid ferric complex salts and at least one selected from dicarboxylic acids and/or monocarboxylic acids. Processing method. 2) The organic acid ferric complex salt is an aminopolycarboxylic acid ferric complex salt.
2. A method for processing a silver halide color photographic light-sensitive material according to claim 1, which comprises processing with a bleach-fix solution which is an iron complex salt and has a free acid having a molecular weight of 350 or more. 3) The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the dicarboxylic acid and/or monocarboxylic acid is an aminodicarboxylic acid and/or an aminomonocarboxylic acid. 4) The aminodicarboxylic acid and/or aminomonocarboxylic acid is at least 2 mol % based on the aminopolycarboxylic acid ferric complex salt in which the free acid has a molecular weight of 290 or more.
A method for processing a silver halide color photographic material according to claim 1, which comprises: