JPH03226751A - Bleach-fix bath for silver halide color photographic sensitive material and processing method using the same - Google Patents

Abstract

PURPOSE:To make improvement in the preservable stability of a bleach-fix bath and to prevent the conversion of a cyan dye to leuco by incorporating respectively specific ratios of thiosulfate and thiocyanate as fixers into this bath. CONSTITUTION:The ferric complex salt of diethylenetriaminetetraacetic acid is incorporated as a bleaching agent into this bath. The thiosulfate is incorporated at least at 1.0 mol per 1l bleach-fix bath and the thiocynate at least at 0.5 mol as the fixer thereof into the bleach-fix bath. Even if soluble silver complexes and iodine ions accumulate, the fixability is substantially unaffected and the rapid processing and lessened replenishing are possible. In addition, the preservable stability of the bleach-fix bath is improved and the conversion of the cyan dye to the leuco is prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a bleach-fix solution for silver halide color photographic light-sensitive materials and a processing method using the same, and more specifically relates to a bleach-fix solution for silver halide color photographic light-sensitive materials and a processing method using the same, and more specifically, a bleach-fix solution for silver halide color photographic materials and a processing method using the same. The present invention relates to a bleach-fixing solution and a processing method that provide excellent and stable processing performance.

[Background of the invention]

Conventionally, so-called bleaching agents for removing image silver from silver halide photographic materials include red blood salt, dichromium salt-resistant,
Oxidizing agents such as persulfates and iron chloride have been used. However, these oxidizing agents have problems in that they are toxic and corrode processing machine components, and are not fully satisfactory in practical terms.

In recent years, a method has been proposed in which an aminopolycarboxylic acid metal j/3 salt is used as an oxidizing agent in a bleaching solution or a bleach-fixing solution since there is no problem with toxicity. However, aminopolycarboxylic acid metal complex salts have the disadvantage of weak oxidizing power and therefore slow bleaching speed of image silver. This method has the disadvantage that the necessary one-bath bleach-fixing process cannot be carried out.

In fact, iron ethylenediaminetetraacetate (m) is considered to have the strongest bleaching edge among aminopolycarboxylic acid metal complex salts.
Complex salts have also been put to practical use as bleach-fixing solutions in the -=· area. However, high-sensitivity silver halide color photographic materials based on silver bromide or silver iodobromide emulsions. In particular, in the case of photographic color papers, photographic dynamic films, and color reversal films that contain silver iodide as silver halide, the bleaching effect is insufficient, and even after processing for a long time, only traces remain. Problems such as image silver remaining and poor desilvering properties, or even dissolving in the processing solution,
There is a problem that the bleaching edge deteriorates significantly when the concentration of aI salt that accumulates with There is a problem in that silver defects are particularly noticeable.

Conventionally, in order to solve these problems, the
Publication No. 46-28 (Publication No. 1, Japanese Patent Publication No. 4G-5
As described in Japanese Patent Application Laid-open No. 5θ, No. 5630/1983, etc., a bleach-fixing solution containing ethylenediaminetetraacetic acid iron (m) complex salt as an oxidizing agent is added with a bleaching accelerating effect.
However, there are problems such as not always achieving a satisfactory bleaching accelerating effect, or the formation of poorly soluble precipitates when silver dissolves and accumulates, making it difficult to use as a practical bleach-fixing solution for very sensitive silver halide color photographic materials. It wasn't Uruchino.

Another method is to use iron ethylenediaminetetraacetate (m)
A method has also been proposed in which complex salts are used in low pH ranges where their bleaching properties are more effective, but the stability of the solution is low because the coexisting thiosulfur and sulfites are easily decomposed. It is also well known that color-forming dyes, especially cyan dyes, tend to undergo leuco formation, resulting in a serious problem of insufficient color development.

To solve this problem, processing at a high pH reduces the amount of cyan leuco dye, but the desilvering property decreases as p)l increases, and the dye due to the coupling between the oxidized form of the developing agent and the residual coupler. There are drawbacks such as staining (referred to as stain), and satisfactory bleach-fixing processing performance cannot be obtained.

As a method to solve the above problem, JP-A-59-14935
84j publication, 59-151154 publication and 5!1
1-186957 and the like discloses a technique using a ferric complex of diethylenetriaminepentaacetic acid at a pH of 5.0 or higher.

Also, JP-A-1983-! Publication No. 32952, 83-954
1.3- in Publication No. 51 and Publication No. 83-95452, etc.
Also disclosed are methods using diaminopropanetetraacetic acid ferric complex salts.

These techniques are certainly superior to the conventionally used ferric complex salt of ethylenediaminetetraacetic acid in terms of bleaching properties and are superior in processing sensitive materials with high silver content. However, when diethylenetriaminepentaacetic acid ferric complex salt is used, the bleach-fixing speed is relatively fast at the beginning of the running process, but as soluble silver complex ions and iodide ions accumulate, trace a! There was a problem that desilvering failures were likely to occur, and unless ffJ+ treatment was performed for a long time, desilvering performance could not be improved and rapid processing could not be performed. In addition, thiosulfate, which is commonly used as a fixing agent, has a slow fixing speed, and unless it is used at a high concentration, a sufficient fixing speed cannot be obtained. There was also the problem that the cyan dye became leuco and the color did not develop sufficiently.

On the other hand, 1,3-diaminopropanetetraacetic acid! When R2 iron complex salt is used, the bleaching edge is even higher than that of diethylenetriaminepentaacetic acid ferric chain pigeon, and desilvering is completed quickly in the early stage of development, and although there is no defective color recovery, it can be reduced to 1.3% in a short time.
-Diaminopropane Tetraacetic acid ferric rust salt and thiosulfate reacted and sulfurized, and it was found that there was a problem in that it could not be put to practical use as a bleach-fix solution.

Therefore, it solves the problem of quick silver source white blade and fixing power, storage stability of bleach-fix solution and prevention of leucoization of cyan dye!
- There is a strong desire for a bleach-fix solution and processing method that can be used in practical applications.

[Problem to be solved by the invention]

Therefore, the object of the present invention is to provide a bleach-fix solution for silver halide color photographic light-sensitive materials that has a rapid silver source white blade and fixing power, has storage stability of the bleach-fix solution, and can prevent cyan dye from becoming leuco, and uses the same. The purpose is to provide a processing method.

[Means to solve the problem]

Undeveloped 'JIS, etc. is a bleach-fix solution for silver halide color photographic light-sensitive materials containing diethylenetriaminepentaacetic acid ferric chain salt as a Ps whitening agent. At least 1 sulfate
．． 1 and at least 0.0 moles of thiocyanate.
It has been found that the above object can be achieved by a bleach-fix solution for silver halide color photographic materials containing 5 mol of silver halide, and a method for processing silver halide color photographic materials using this bleach-fix solution.

It has also been found that the object of the present invention can be achieved more effectively by containing at least 0.75 mol of thiocyanate per bleach-fix solution.

Furthermore, in the processing power method, the replenishment amount of the bleach-fixing solution was 7.0-7.0 cm per 100 cm of silver halide color photographic light-sensitive material.
It has been found that the object of the present invention can be more effectively achieved by standing the device upright.

[Effect]

The combination of diethylenetriaminepentaacetic acid W42 iron complex salt and thiocyanate is disclosed in JP-A-48-3340 and JP-A-1-234848, etc., and the combination of thiocyanine #salt and thiosulfate is also disclosed. JP-A-46-3
It is disclosed in Publication No. 340 and the like.

However, unlike the case where thiosulfate is used as a fixing agent, a bleach-fix solution that simply combines diethylenetriaminepentaacetic acid ferric complex salt and thiocyanate produces silver thiocyanate, which cannot be easily eluted from the photosensitive material. However, there is a problem in that fixing defects occur as a result.

To solve this problem, a technique that adds a large amount of polyvinylpyrrolidone to the bleach-fix solution or the next bath to prevent the formation of silver thiocyanate, or a technique that reprocesses by installing a treatment bath containing thiosulfate in the next bath. It has been known.

However, with the former method of adding a large amount of polyvinylpyrrolidone, there are problems such as polyvinylpyrrolidone sticking to the surface of the photosensitive material and reducing drying properties, sticking to rollers etc. and causing jamming, or adhesion of the photosensitive materials to each other. be.

In order to solve these problems, it may be possible to provide a rinsing facility, but this has the drawback of increasing costs. The latter method of providing a thioic acid salt-containing treatment bath as the next bath is undesirable because it complicates the treatment and goes against the demands for compactness, and the reality is that it has not yet been put to practical use.

On the other hand, even if thiosulfate and thiocyanate are used as a fixing agent as disclosed in JP-A No. 48-3340, the object of the present invention can be achieved as long as ferric complex salt of ethylenediaminetetraacetic acid is used as a bleaching agent. Can not.

That is, in the present invention, by using thiosulfate and thiocyanate as fixing agents at a certain concentration or more,
We have discovered the fact that the disadvantages of each are offset and the fixing speed is further improved.Furthermore, even if soluble silver complexes and iodide ions accumulate, the fixing performance is hardly affected, and moreover, rapid processing and low replenishment are possible. While discovering that it is possible,
In addition, there is a bleaching blade in the bleach-fix solution for bleaching, and it reacts with thiocyanate-resistant salts such as ferric salt of 1,3-diaminopropanetetraacetic acid and ferric salt of glycol ether diaminetetraacetic acid to form iron thiocyanate. It was discovered that diethylenetriaminepentaacetic acid ferric complex salt is excellent as a stable bleaching agent that does not cause any sulfurization due to formation or reaction with thiosulfate, and by using these in combination, the present invention was completed. It is.

[Structure of the invention]

The present invention will be explained in detail below.

The bleaching agent used in the bleach-fixing solution of the present invention is diethylenetriaminepentavinegar ferric (hereinafter referred to as ↑PAFe).
(abbreviated as (m)) is a complex salt. This DTPAFe (OI
) Complex salts include sodium salts, potassium salts, and ammonium salts5
Ammonium salts are preferably used from the viewpoint of the purpose of the present invention and solubility.

The amount of DTPAFe (m) complex salt added is based on the bleach-fix solution lfL.
It is preferably contained in a range of 0.1 mol to 2.0 mol, more preferably in a range of 0.15 to 1.0 mol.

In the bleach-fix solution of the present invention, it is preferable to use the complex salt TPAFe (m) alone, but the following bleaching agents may be used in combination without impairing the effects of the present invention. Bleaching agents that can be used in combination Examples include ferric complex salts (tM of ammonium, sodium, potassium, triethanolamine, etc.) of the following compounds.

(A-1) (A-2) [^-13] [^-4] [A-5] [^6] [^-17] Ethylenediaminetetraacetic acid trans-1,2-cyclohexanediaminetetraacetic acid dihydroxyethylglycine Acid ethylenediaminetetrakismethylenephosphonic acid nitrilotrismethylenephosphonic aciddiethylenetriaminepentakismethylenephosphonic acidethylenediaminediorthohydroxyphenylacetic acid (A-8) Hydroxyethylethylenediaminetriacetic acid (A-9) Ethylenediaminedipropionic acid (A-
1(1) Ethylenediaminediacetic acid (A-11)
Hydroxyethyliminodiacetic acid (A-12) Nitrilotridissolution (A-13) Nitrilotripropionic acid (A-14)
) Liethylenetetraminehexaacetic acid (A-15)
Ethylenediaminetetrapropion Ugly The bleach-fixing solution of the present invention includes imidazole and its derivatives described in Japanese Patent Application No. 83-481331 or the general formula CI)
Containing at least one of the compounds represented by (IX) to (IX) and their exemplary compounds can have an effect on rapidity.

In addition to the bleaching accelerators mentioned above, the exemplified compounds described in JP-A-62-1234511, pages 6313 to 655, and the exemplified compounds described in JP-A-83-17445, pages 22 to 8825, Exemplary compounds and the like can also be used in the same manner.

These bleach accelerators may be used alone.

Two or more types may be used in combination, and the amount added is generally in the range of about 0.0 I to 100 g per 11 bleach-fixing solutions, more preferably 0.05 to 50 g, particularly preferably 0.0 I to 100 g.
05-15g.

When adding a mountain-opening accelerator, it may be added and dissolved as is, but it is common to dissolve it in wood, alkali, organic acid, etc. before adding it, and add methanol, ethanol, acetone, etc. as necessary. It can also be added after being dissolved in an organic solvent.

The processing temperature of the bleach-fix solution is preferably 20°C to 50°C, preferably 25°C to 45°C.

The pH of the bleaching solution is preferably 6.0 to 9.0, more preferably 6.5 to 8.5, so that the effect of the present invention becomes more pronounced. That is, when the pH is low, the color of the bleach-fix becomes slightly coppery, and the formation of iron thiocyanate is observed, and when the pH is high, it affects the desilvering property, but when the pH is 8.0 to 8.0, It has good permeability, color reversibility, and almost no formation of iron thiocyanate.

Note that p)I of the unreleased bleach-fix solution J is the pH of the processing tank during processing of the silver halide photosensitive material, and is different from p)I of the so-called replenisher.

It is generally preferable to add a halide such as ammonium bromide to the bleach-fix solution, and it may also contain various optical brighteners, antifoaming agents, or surfactants.

The replenishment amount of the bleach-fix solution in continuous processing is preferably 7.0 ml or less, more preferably 8.0 ml or less per $4+00 cm of silver halide color photographic light-sensitive material, and even with such a low replenishment, desilvering properties and Good recoloring properties. That is, according to the present invention, it is possible to sufficiently reduce replenishment.

Both thiosulfate and thiocyanate are used as the fixing agent contained in the bleach-fix solution.

The amount of thiosulfate added is at least 1 per 11 parts of the bleach-fix solution.
．． 0 mol, preferably in the range of 1.0 to 3.0 mol, more preferably in the range of 1.2 to 2.5 mol. In addition, the amount of thiocyanate added is as follows:
at least 0.5 mol, preferably 0,
It is in the range of 5 to 4.0 mol, more preferably 0.75 mol.
~3.0 mol.

If the amount of thiosulfate added is less than 1.0 mol/ml and the amount of thiocyanate added is less than 0.5 mol/ml, the desilvering property will be insufficient and the object of the present invention cannot be achieved. In this case, the purpose of the present invention cannot be achieved simply by using thiosulfate and thiocyanate together, but the purpose of the present invention can be achieved when thiosulfate and thiocyanate are contained at a certain concentration or higher.

Examples of thiosulfates include sodium thiosulfate, ammonium thiosulfate, potassium thiosulfate, and the like, and examples of thiocyanine salts include ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, and the like.

The bleach-fix solution consists of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.p)! A single buffering agent or two or more types of buffering agents may be included.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is preferable to contain a large amount of a rehalogenating agent such as ammonium bromide, and compounds known to be usually added to bleach-fix solutions such as alkylamines and polyethylene oxides may be added as appropriate.

To increase the activity of the bleach-fix solution, air or oxygen may optionally be blown into the processing bath and into the processing replenisher storage tank, or a suitable fermenting agent such as hydrogen peroxide, bromic acid may be added. Salts, persulfates, etc. may be added as appropriate.

In the present invention, the amount of silver accumulated in the bleach-fix solution.

Even if the amount of accumulated iodine increases (for example, about 5 g/l of Ag', about 5 g/l of I-0), the object of the present invention can be effectively achieved without deteriorating the desilvering property.

When carrying out the method of the present invention, silver may be recovered from the bleach-fix solution by a known method. Publication No. 52-73037, narrow patent 2.331,
220 specification), ion exchange method (Jikai 1 scoop 51-
17114, German Patent Note 2,548,217) and metal substitution method (British Patent No. 1,353,8)
(described in the specification of No. 05) etc. can be effectively used.

It is particularly preferable to recover silver in-line from the tank solution, as this improves suitability for rapid processing, but it is also possible to recover silver from the overflow waste solution and reuse it.

For the bleach-fixing solution, Japanese Patent Application No. 63-48931 f5
A compound represented by the general formula [FAI] described on page 56 and exemplified compounds thereof may be added.

The compound represented by the general formula [FAI] described in the same specification is described in U.S. Pat. No. 3,335,181 and U.S. Pat.
(It can be synthesized by a general method as described in the specification of No. 1,718. These compounds represented by the general formula [FAI] may be used alone or in combination of two or more. good.

Further, good results can be obtained when the amount of the compound represented by the general formula [FAI] ranges from 0.1 g to 200 g per 14 of the treatment liquid. In particular, the range of 0.28 to 100 g is preferable, and the range of 0.5 g to 50 g is particularly preferable.

Sulfites and sulfite-releasing compounds may be used in the bleach-fix solution; specific exemplary compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, metabisulfite, Examples include potassium sulfite, sodium metabisulfite, ammonium metabisulfite, and the like.

Furthermore, compounds represented by the general formula [B-1] or [B-2] described on page 60 of Japanese Patent Application No. 63-48931 are also included.

These sulfites and sulfite-releasing compounds preferably range from 0.12 mol to 0.65 mol, particularly preferably from 0.15 mol to 0.50 mol, as sulfite ion per 11 bleach-fix solution, and especially preferably from 0.15 mol to 0.50 mol, especially 0. ,20mol~0.4
A range of 0 mol is preferred.

The total treatment time with the bleach-fix solution is preferably 4 minutes 30 seconds or less, more preferably 10 seconds to 3 minutes 45 seconds, particularly preferably 20 seconds to 3 minutes 15 seconds.

In the processing method of the present invention, it is preferable from the viewpoint of rapid processing suitability to apply forced liquid stirring to the bleach-fix solution.
Forced liquid stirring here means 1. It means adding a stirring means to forcibly stir the liquid instead of the normal diffusion movement of the liquid.
No. 0 and Japanese Patent Application Laid-Open No. 1-208343.

Color developing agents used in the color development process include:
There are aminophenol compounds and p-phenylenediamine compounds, but in the present invention, p-phenylenediamine compounds having a water-soluble group are preferred.

Such a water-soluble group has at least one on the 7-mino group or benzene nucleus of the p-phenylenediamine compound, and a specific water-soluble group is -(CHz) n-
C) 120H (C1(2)s-NllSO2-(CHz) 1l-C
H3゜-(CH2)@-0-(CH2) Tl-CH3
, -(C)1zc)I2(1)nc, H21+ (a+
and n each represent an integer of 0 or more, ) , -COO
)l group, -9(hH group, etc.) are preferred.

Specific exemplary compounds of the color developing agent that are frequently used in the present invention are shown below.

Below is the margin [Example color developing agent] (A 7)! 1011. C, YC, I1.0+1 NH8 (A-8) 0・IIs＼ノ山5OsH にN11゜(A-9) 1]・0・N10・11・So・(1 Among the color developing agents exemplified above Preferred examples for use in the present invention are example Nos. (A-1), (^-2), (A-
3), (^-4), (^-6), (A-7) and (A
-15).

The above color developing agent is usually 1i! Acid salts, sulfates.

It is used in the form of salts such as p~toluenesulfonate.

The color developing solution used in the color development process contains alkaline agents commonly used in developing solutions, such as sodium hydrate, potassium hydroxide, ammonium hydroxide, sodium carbonate,
Potassium carbonate, sodium sulfate, sodium metaborate or borax can be included. Furthermore, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, development UA moderators such as citradinic acid, and preservatives such as hydroxylamine and hydroxylamine derivatives (such as diethylhydroxylamine). , a hydrazine derivative (for example, a hydrazine derivative), or a sulfite salt.

Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~I3.

The color developer may optionally contain antioxidants such as tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, pyrogallol!
, 3-dimethyl ether, etc. may be contained.

Used as a sequestrant for metal ions in color developing solutions.

Various chelating agents can be used in combination.For example, the chelating agents include 7minopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, and aminotri(methylenephosphonic acid). acids) or amine polyphosphonic acids such as ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid,
Examples include phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-)licarponic acid, and polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid.

The preferred replenishment amount of color developing solution in continuous processing is preferably 9.0-l or less per 100 cm of light-sensitive material for color negative films, and more preferably 2.5 m
fL ~ 8.0 x, more preferably 3.0 ■ love ~
I saw it on 7,01.

In the present invention, the light-sensitive material is preferably processed in a stabilization process subsequent to the bleach-fix process.

In continuous processing, the amount of replenishment of the stabilizing solution is preferably 1 to 80 times, particularly 2 to 80 times, the amount of sunlight brought in from the pre-bath per unit area of color photographic light-sensitive material to be processed.
The concentration of the pre-bath component (overnight fixer) in the stabilizing solution is more preferably 11,500 or less, particularly preferably 171,000 or less in the final stabilizing tank. Furthermore, from the viewpoint of low pollution and liquid storage stability, it is preferably 1/500 to 1/10001)0, more preferably I/20QO to 1150000.

The amount brought in from the pre-bath differs depending on the type of photosensitive material 2, the conveyance speed of the automatic developing machine, the conveyance length, the method of squeezing the surface of the photosensitive material, etc. In the case of color photosensitive materials for photography, the amount carried in is normally 50 mfL/m' to 1501 lines/m', and the effective replenishment amount for this amount brought in is 50 mfL/m'
~4.1/rn'(7), and the replenishment amount with a particularly remarkable effect is in the range of 200 h/rn' to 1500 h/m''.

The stabilizing species is preferably composed of a plurality of hinoki cypresses, preferably from 2 to 6 hinoki, particularly preferably from 2 to 3 hinoki, even more preferably 2 hinoki, using a counter current method (after bathing). It is preferable to use a method in which the water is supplied and overflowed from the pre-bath.

The treatment temperature for the treatment with the stabilizing liquid is preferably 15 to 60°C, more preferably in the range of 2G to 45°C.

The pH value of the stabilizing solution is preferably in the range of p)I 4.0 to 9.0, more preferably in the range of pH 4.5 to 9.0, particularly preferably p)I, for the purpose of improving image storage stability. ) I ranges from 5.0 to 8.5.

By adding hexamethylenetetramine or a triazine compound to the stabilizing solution, the generation of floating substances can be effectively prevented.

It is preferable that the stabilizing liquid contains a metal salt in combination with a chelating agent. Examples of such metal salt include Ba.

Ca, Ce, Go, 1l, La, ) 1l, Ni,
Sun i, pb, Sn, Zn.

T1. Zr, Mg, All or St gold 11h
1M, and can be supplied as an inorganic salt such as a halide monohydroxide, sulfate, carbonate, phosphate, acetate, or a water-soluble chelating agent. The amount used is 1x per li of stabilizer.
The range is preferably from 10 to 1X10-1 mole, more preferably from 4X10-4 to 2X10-2 mole.

The stabilizing solution contains organic acid salts (citric acid, acetic acid, co/% phosphoric acid,
oxalic acid, ammonium, aromatic acid, etc.), pH:iJ adjusters (phosphoric acid, borate, hydrochloric acid, sulfate, etc.), surfactants, preservatives, etc. can be added. These compounds may be added in any combination of amounts that are necessary to maintain the pH of the stabilizing bath and do not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. do not have.

Preferably used anti-spill agents in the stabilizer include hydroxybenzoic acid ester compounds, 2-phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds,
Car/hemate compounds, morpholine compounds, quaternary phosphonium compounds.

These are ammonium compounds, urea compounds, inxasol compounds, propatoolamine compounds, sulfamide compounds, amino acid compounds, diactive halogen-releasing compounds, and penttriazole compounds.

In addition, the compounds preferably used among the above-mentioned anti-spill agents are:
These are phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen-releasing compounds, and penttriazole compounds. Furthermore.

Particularly preferred are phenolic compounds from the viewpoint of liquid storage stability.
These are thiazole-based compounds, active halogen-releasing compounds, and penztriazole-based compounds.

The amount of anti-piping agent added to the stabilizing solution is 0.0 per liter of stabilizing solution.
The range is preferably from 0.001 to 50 g, more preferably from 0.00 to 50 g.
It is used in the range of 0.005 to 10 g.

In the treatment of the present invention, silver may be recovered from the stabilizing solution by the above-mentioned method, and the stabilizing solution may also be subjected to ion exchange treatment, electrodialysis treatment (see Japanese Patent Application No. 59-98352) or reverse osmosis treatment (Japanese Patent Application No. (See No. 59-!38532), etc., and it is also preferable to use water that has been deionized in advance. This is because it measures the propensity to save images.
As a means of deionization treatment, Ca,
Any material may be used as long as it reduces Mg ions to 5 pp- or less.

For example, ion exchange resins and reverse osmosis membranes, which are preferably treated alone or in combination, are described in detail in Kokai Technical Report No. 87-11184.

The salt concentration in the stabilizing solution is preferably 1000 pp@ or less.

More preferably it is 800PP- or less.

The processing time for the stabilizing solution is preferably 2 minutes or less, more preferably 1 minute 30 seconds or less, particularly preferably 1 minute or less from the viewpoint of rapid processing.

The stabilizing liquid may contain a surfactant. As surfactants, general formulas [I] to [I! ] and water-soluble organic siloxane compounds.

Silver halide color photographic material (hereinafter referred to as “
The silver halide grains used in the "photosensitive material" or "sensitive material" may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver iodobromide is preferably used.

The average silver iodide content of all silver halide emulsions in the light-sensitive material is preferably 10.1 to 15 mol%, more preferably 0.
．． It is 5 to 12 mol%, particularly preferably 1 to 10 mol%.

The average grain size of all the silver halide emulsions in the light-sensitive material is preferably 2.0 mm or less, more preferably 0.1~! , θμ garden.

When the silver halide emulsion contains grains having an average value of grain size/grain thickness of less than 5A, it is preferable from the viewpoint of desilvering properties that the grain size distribution is monodisperse.

A monodisperse silver halide emulsion is a monodisperse silver halide emulsion with an average grain size r centered around 1.
Refers to silver halide grains in which the weight of 1M halide contained within a grain size range of 20% is 60% or more of the total weight of silver halide grains,
It is preferably 70% or more, more preferably 80% or more.

Here, the average particle size r is defined as the particle size ri when the frequency of particles with particle size ri and ``i3 niX ri' is maximum (3 significant figures, minimum 4 digits). Discard 5
people).

In the case of a spherical silver halide grain, the grain size referred to here means the diameter thereof, and in the case of a grain having a shape other than spherical, the diameter when its projected image is converted into a circular image of the same area.

The particle size can be obtained, for example, by photographing the particle with an electronic S microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print (number of particles measured). (assumed to be at least 1000 indiscriminately).

Particularly preferred highly monodisperse emulsions are those in which the breadth of the distribution defined by the average grain size is 20% or less, more preferably 15% or less.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0] planes to [1,1,1,] planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell y1i) in which the inside and outside are different. These silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside one grain. (See No. 170070/1983) can also be used.

The silver halide grains may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, seed grains may be produced using an acidic method, and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size. ．． It is preferable to control PAg and the like, and to sequentially and simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in, for example, JP-A No. 54-48521.

The preparation of silver halide grains is preferably carried out as described above.
In this specification, it is referred to as a silver halide emulsion.

These silver halide emulsions include activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous sensitizers, thiourea dioxide, etc. , polyamine, etc.: 3! Metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or water-soluble materials such as ruthenium, palladium, platinum, rhodium, iridium, etc. sensitizers such as ammonium chloroparadate, potassium chloroaurate, and sodium chlorovaradate (these types act as sensitizers or fog suppressants depending on the amount). ) or the like alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.).

The silver halide emulsion is chemically ripened by adding a sulfur-containing negative compound, and during or after this chemical ripening, a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group is produced. You may contain at least one kind of.

Silver halide increases photosensitivity by 1 for each desired wavelength range.
For example, 5 x 1G-8 to 3 x 10-3 mol of a sensitizing dye may be added to 1 mol of silver halide for optical sensitization. Various sensitizing dyes may be used. In addition, each sensitizing dye can be used alone or in combination of two or more.

In addition, the light-sensitive material contains a coupler, that is, a compound capable of forming a dye by reacting with an oxidized form of a two-color developing crude drug, in each of the five red-sensitive silver halide emulsion layers, the blue-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer. It is preferable to include it.

Yellow couplers that can be used include closed ketomethylene compounds and active point -so-called 2-equivalent couplers.
0-7 aryl substituted couplers, active point -0-acyl substituted couplers, active point hydantoin compound substituted couplers, active point urazole compound substituted couplers, and active point substituted couplers with succinimide compounds.

Active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -O-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. A specific example of a yellow coupler using
, No. 057, No. 3,265,508, No. 3.408,
194 No. 2 No. 3,551,155, No. 3,582,3
No. 22, No. 3,725,072 No. 2 No. 3,891,44
No. 5, No. 3.933501, No. 4,022,820, No. 4,326,024, No. m4.401,752,
West German Patent No. 1,547,888, West German Application Publication No. 2,21
No. 9,917, No. 2,281,381 No. 1 No. 2,414
, No. 008, British Patent No. 1,425,020, No. 1,4
No. 78,780, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 4
No. 7-26133, No. 48-73147, No. 51-1
No. 02636, No. 50-6341, No. 50-1233
No. 42, No. 50-12342, No. 51-21827, No. 50-876509, No. 52-82424, No. 52-115219, No. 58-95346, JP-A No. 1-180542, etc. I can list things.

Examples of magenta couplers that can be used include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. These magenta couplers are not only 4-equivalent couplers like the yellow couplers.

2 Specific examples of magenta couplers that can be used include U.S. Pat. No. 2,800,788;
No. 2,983,608, No. 3,082,653, No. 3, No. 127.269, No. 3,311,478, No. 3,418,391, No. 3,519,429, No. 3
, No. 558,319, No. 3,582,322, No. 3,
No. 815,508, No. 3,834,1108, No. 3,
No. 891,445, No. 4,310,619, No. 4,3
No. 51,897, No. 4,500.830, No. 4,54
0,854, West German Patent No. 1,810,484, West German Patent No. m111 (OLS) No. 2,408.81115, No. 2,417,945, No. 2,424,487, Japanese Patent Publication No. 40-8031 , Japanese Patent Publication No. 51-20826, M5
No. 2-58922, No. 49-129538, No. 49-
No. 74027, No. 50-159336, No. 52-42
No. 121, No. 49-74028, No. 5o-60233
Examples include those described in No. 51-26541, No. 53-55122, No. 60-43659, and European Patent No. 73636.

Examples of cyan couplers that can be used include phenolic and naphthol couplers. These cyan couplers may be not only 4/15 couplers like the yellow couplers but also 2-equivalent couplers. Specific examples of cyan couplers that can be used include U.S. Pat.
No. 9,929, No. 2,434.272, No. 2,474
, No. 293, No. 2,521,908, No. 2.895,
No. 828, No. 1,034,892, No. 3,311,4
No. 78, No. 3,458,315, No. 3,478,56
No. 3, No. 3,583.971, No. 3,591,383
No. 3,767.411, No. 3772.002,
No. 3,933,494, No. 4,004. ! 112!3
No. 4,052,212, No. 4,146,396, No. 4,228,233, No. 4.2!3Ei, 200
No. 4,334,001, No. 4.327173,
4,451,559, 4,427,767 1 European Patent No. 121365A, 161626A, West German Patent Application (OLS) 2,414,830, 2,45
No. 4,329, JP-A-48-5983, JP-A No. 51-26
No. 034, No. 48-5055, No. 51-146827
Examples include those described in Japanese Patent Publication No. 52-69624, No. 52-90932, No. 58-95348, and Japanese Patent Publication No. 49-11572.

A coupler such as a colored magenta or colored cyan coupler or a polymer coupler may be used in combination in the silver halide emulsion layer and other photographic constituent layers.
No. 9-193611 (see JP-A-61-72235)!
@), and regarding the polymer coupler, please refer to Japanese Patent Application No. 59-172151 (Japanese Unexamined Patent Publication No. 61-50) filed by the present applicant.
143).

In the present invention, in particular, JP-A-83-108655
Magenta couplers represented by the general formula [M■] as described on page 26 of the specification (Specific examples of these magenta couplers include No. , 1-No., 77), and the general formula [C-I
] or [C-II] (specific examples of cyan couplers are (C″-1) to (C″-82) described on pages 37 to 42 of the same specification).

(C″-1) to (C″-38)), the high-speed yellow couplers also described on page 20 (specific examples of yellow couplers include those described on pages 2! to 26 of the same specification). (y'-t) to (Y'-39) and JP-A-1-1
(Y
-1) to (Y-31)) in combination with the light-sensitive material of the present invention is preferred from the viewpoint of the desired effects of the present invention, especially from the viewpoint of rapidity.

Furthermore, the effects of the present invention are particularly effective in terms of speed and desilvering properties, such as those described in Patent No. 11/(E13-32501 (P232 to P232).
278) BAR compounds (exemplary compounds (1) to (77)
) is also a preferred embodiment of the present invention.

When using a photosensitive material containing high silver chloride, it is preferable to use a nitrogen-containing heterocyclic mercapto compound in combination.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds are described in JP-A-83-10Ei855 1j Particulars, Nos. 42-4.
Examples include (I'-1) to (I'-87) described on page 5.

The light-sensitive material may contain various other photographic additives. For example, Research Disclosure Magazine 1
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, one-color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, as described in No. 7843. Agents etc. can be used.

In the photosensitive material, gelatin is preferably used as the woody colloid used to condition the emulsion.

In addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose conductors such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, and polyacrylamide, etc. Any single or copolymer synthetic woody polymers are included.

Supports for photosensitive materials include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and transparent supports with a reflective layer. For example, a glass plate or the like may be used, and other ordinary transparent supports may be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers. Also, U.S. Patent Nos. 2,781.731 and 2,94
1. ．． It is also possible to use a simultaneous coating method of two or more layers by the method described in No. aH.

The coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color color negative photographic light-sensitive material, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer are sequentially applied from the support. It is preferable to arrange the blue-sensitive silver halide emulsion layers, and each of these light-sensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material processed according to the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, protective layer, antihalation layer, etc. They can be used in appropriate combinations as layers. In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

In the method for processing a photosensitive material of the present invention, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method, color negative film, color paper, color positive film, color for slides, etc. It can be applied to any photosensitive material such as reversal film, color reversal film for movies, color reversal film for TV, and reversal color paper.

〔Effect of the invention〕

According to the present invention, it is possible to provide a bleach-fix solution for photosensitive materials that has a quick silver source white blade and fixing power, has storage stability of the bleach-fix solution, and can prevent leucoization of cyan dye, and a processing method using the same.

[Examples] The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited to these examples.

Example 1 A bleach-fix solution was prepared as follows.

Ferric ammonium salt of organic acid (listed in Table 1) 0.3E ammonium sulfite (40% solution) 30s fixative (listed in Table 1) 3.0mol Aqueous ammonia or glacial acetic acid to pH 7.5 Adjust the total amount to 1 liter.

Pour the above bleach-fix solution into a narrow-mouth bottle with an opening area (contact area with air per 1 liter of processing solution) of 15 cm2/4 at 50°C.
The formation of sulfides and the external color of the bleach-fix solution after storage for days were evaluated.

However, the formation of sulfides was evaluated according to the following criteria.

■ No sulfides are observed.

0 A slight amount of floating matter is observed on the liquid surface.

Δ A slight amount of sulfide is observed.

X A small amount of sulfide is observed.

XX A large amount of sulfide is observed to be generated.

The results are shown in Table 1.

Table 1 EDTAFe (m) DTPAFe (m) P[1TAFe ([II) GEDTAFe (m): Ethylenediaminetetraacetic acid ferric ammonium salt Nidiethylenetriaminepentaacetic acid ferric ammonium salt: l, 3
- Diaminopropane tetraacetic acid Mffi ferric ammonium salt nigericol ether diamine tetraacetic acid ferric ammonium salt As is clear from Table 1, EOTA is
Fe(III), DTPAFe(III),
Using a bleach-fix solution using EDTAFa (m) and thiocyanate as a fixing agent, PDTAFe (I[
A bleach-fix solution containing I) as a bleaching agent is good, but the external color of the solution shows that EDTAFe (III) and GEDTAFe
The bleach-fix solution containing (m) in combination with thiocyanate turned slightly coppery in color, confirming the production of iron thiocyanate.

Example 2 The amounts added in silver halide photographic materials are expressed in g per lrn' unless otherwise specified. Silver halide and colloidal steel are expressed in terms of silver.

Sample 1 of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample 1 1st layer: Antihalation layer Black colloidal steel 0.20 Ultraviolet absorber (UV-1) 0.20 Colored coupler (C
C-+) Colored coupler (CM-2) High boiling point solvent (oil-f) Gelatin 2nd layer: Intermediate layer ultraviolet absorber (UV-1) High boiling point solvent (oil) Gelatin 3rd aF: Low sensitivity red sensitivity Emulsion layer Silver iodobromide emulsion (Es-1) Silver iodobromide emulsion (Es-2) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) ...0 .05 ...0.08 ...0.20 ...1.8 ...0.01 ...0. Ol...1.2...■, 0...0.5...2.2 Xl0 (7s/1111 mol) Mountain 2.5XIO (t/silver!mol)...0. 5X10 (Moh/Ftn) Cyan coupler (C-4') Cyan coupler (C-2')...1.2...0.3 Colored cyan coupler (ILI knee 1)...0.0
5 DIR compound (Tol) High boiling point solvent (oil-1) Gelatin...0.002...0.5...1.3 4th layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion ( Ea-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) Cyan coupler (C-1') Cyan coupler (C-2') Cyan coupler (C-3) ') Colored cyan coupler DIR compound (El-2) High boiling point solvent (oll 1) ...2.1 ...2.2X1G (mol/! [1 moA) ...2.0XIO (mol/silver) 1 mole) ...0. I Xl0 (MoA/ff11 mol) ...0.20 ...0.03 ...! , 15 (CC-t)...0.015...0.05...0.5 Gelatin...1.4 5th layer: Intermediate layer gelatin...0.4 6th layer: Low Sensitivity Green-sensitive emulsion layer Silver iodobromide emulsion (El-1) Sensitizing dye (S-4) Sensitizing dye (S-5) Magenta coupler (Ml)...0.9...5-oxi.

(mol/silver! mol)...2.0X10 (mol/silver 1 mol)...0.45 Colored magenta coupler (ON-1)...0.05 DIR compound (D-3) DIR compound ( El-4) High boiling point solvent (oil-2) Gelatin 7th layer: Intermediate layer gelatin high boiling point solvent (oil-1) ...0.015 ...0.020 ...0.5 ...1 .1 ...0.8 ...0.2 8th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (El-3) Sensitizing dye (S-13) Sensitizing dye (S-7) Sensitizing dye (S-8) Magenta coupler Magenta coupler (M-2) (M-3) ...1.4 ...1.5XIO (Mo4/[1Mh) ...2.5 Xl0 (Mole/Silver IEA)...0.7X10 (MoA/#U mole)...0.08...O0!8 Colored magenta coupler (C1ll-2)...0.
05 IIIR compound (3) High boiling point solvent (oil-3) Gelatin...0. Ol...0.5...1.3 9th layer: Yellow filter layer Strong color colloid silver stain inhibitor (SC-1) High boiling point solvent (oil-3) Gelatin...0.12... 0.1 ...0.1 ...0.8 1st θ layer: U layer: Low sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (El-1) Silver iodobromide emulsion (Em-2) Sensitive dye (S-1n) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (Ail-2) High boiling point solvent (Ail-3) Gelatin High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Ea- 4) Silver iodobromide emulsion (Ea-1) Sensitizing dye (S-9) Sensitizing dye (S-tO) Yellow coupler (Y-1) Yellow coupler (Y-2) High boiling point solvent (oil-3) Gelatin...0.32...0.24...7.0XlO (moA/silver 1 moA)...0. θ...0.2...0.01...O0!5...1.2...0.50...0.27...1.3X10 (7h/silver 1 mo h) ...3.0 Silver bromide emulsion (average grain! 1.0.08 m, Agl ultraviolet absorber (
UV-1) Ultraviolet absorber (tlV-2) High boiling point solvent (oil-1) High boiling point solvent (oil-4) ...0.30 2.5Peng O1%) ...0. lO...-0,05...0.1...0.1...0.5 Formalin scavenger-013-2)...0,2 Gelatin 13th layer: 2nd protective layer surfactant Agent (Su-1) ...1.2 ...0.005 Alkali-soluble matting agent (average particle size 2) ...0.10 Cyan dye (
AIG-1) Magenta dye (Allll-1) Slip agent (IIAX-1) Gelatin...0.01...0. Ol...0.04 ・-0, 7 In addition to the above composition, each layer contains coating aid 5u-2, dispersion aid 5u-3, hardener) 1-1 and H-2, Preservative old-1. Stabilizer 5tab-1, antifoggant ＾F-1゜A
F-2 was added.

Em-1 Average grain size 0.45gm, average silver iodide content e, oH,
, % monodisperse surface low silver iodide content emulsion m-2 Average grain size 0.33#Lm, average silver iodide content 2.5 mol % emulsion emulsion Em-3 with uniform composition and monodispersity Diameter 0.78μ, average silver iodide content 6.0mol%
Monodisperse surface-low silver iodide-containing emulsion 1-4 Average grain size 0. I35ILm, average iodized steel content? , O
, h% monodisperse surface low silver iodide containing emulsions E@-I, Em-3 and El-4 are disclosed in JP-A-80-138.
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to the publications of No. 5ff8 and No. 61-245151.

Furthermore, for Em-1-Ea+-4, the average value of particle size/particle thickness was 10, and the width of particle distribution was 12%, 10%, and 11%, respectively.

-4 6 -9 -10 3' C, l+.

11 -1 5 5 0M-1 l -2 5 0I+ 01薔H U■ 11 C,IP(L) V-2 C,lls -2 (CIIJxS03K u aOsS I C-C00CI+, (CI', CF,), 11C-C0
0C11, (CI!, CF,)3+111゜u NaO,S 1 C-COOCIIl,ff Ut COOC,11,? u-3 c 011 11 A I C-1 ΔIM tab-1 0I+ P 1 i1 P 11-4 The film sample thus prepared was exposed to constant light and processed under the following conditions.

Processing time Processing temperature Color development
3 minutes 15 seconds 38°C fixation 3 minutes! 5 seconds 38℃ stabilization (3 tank h skate) 1 minute
Dry at 38℃ 1 minute 4
0°C to 80°C Color developer Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 3.0g Sodium bromide
1.3g potassium iodide
! , 2mg hydroxylamine sulfate 2.5g sodium chloride
0.684-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.081-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Hydroxylation Potassium 1.28 Add water to 1
1 and pH using potassium hydroxide or 20% sulfuric acid.
Adjust to 10,00.

Page 1 Cliff 1 The bleach-fix solution of Example 1 (before storage and after storage) was used (listed in Table 2).

However, each bleach-fix solution contains 5.0g of silver! , 0.5 g/l of potassium iodide was added.

Missing main lid 1.2-benzthiazoline-3one G, 1
゜Siloxane surfactant 0.8g Hexahydro-1,3,5-tris(2-hydroxyethyl)-5-triazine 0.3g Hexamethylenetetramine 0.2g Add water to make the total bi11, and add 50% sulfuric acid or P with potassium hydroxide
Adjust to H7.0.

After the treatment, the exposed area was divided into two parts, and one part was used to measure the amount of remaining steel using fluorescent X-rays. In addition, the other sample was treated with the following treatment liquid and treatment method, the maximum transmission density (R concentration) before and after the treatment was determined, and the difference was taken as the recoloring property.

Koyu lid EDTAFe (m) Ammonium salt 1 o
Add og water to bring the total volume to 1fi, and adjust the pH to 8.0 with aqueous ammonia or glacial acetic acid.

Oyu store It was treated at 38°C for 5 minutes.

The results are shown in Table 2-1.2-2.

Table 2-1 Table 2-2 Maximum permeation density after this treatment - Maximum permeation density before treatment 2-
As is clear from the results in 1.2-2, thiosulfate sa! is used as a fixing agent. and thiocyanate in combination, and DTPAFe (III) and PDTAFs (m
) has good desilvering properties before storage.

The defective color recovery has been improved, but after storage, PDTAFs (
It can be seen that when m) was used, there was no desilvering at all, and there was also a large defect in color restoration.

Therefore, from Examples 1 and 2, a bleach-fix solution having the composition of the present invention, that is, diethylenetriaminepentaacetic acid ferric complex salt is used as a bleaching agent, and thiosulfate group and thiocyanate at a certain concentration or more are used as a fixing agent. It can be seen that the object of the present invention is thereby effectively achieved.

Example 3 In the bleach-fix solution of Example 2, desilvering properties were evaluated in the same manner as in Example 2, using diethylenetriaminepentaacetic acid ferric complex salt as the bleaching agent and varying the amount of fixing agent shown in Table 3. Ta.

The results are shown in Table 3.

Table 3 As is clear from the results in Table 3, even if thiosulfate or thiocyanate is used alone or in combination with thiocyanate and thiosulfate, if the amount added is outside the scope of the present invention, the desilvering property will be affected. It can be seen that there is a significant difference in terms of desilvering properties, especially in terms of desilvering properties.

Example 4 In Example 3, bleach-fix solution 3-5.3-I+.

The p)I of the bleach-fix solution was changed as shown in Table 4 using Example 3-15, and the same evaluation as in Example 2 was performed.

The results are shown in Table 4.

Table 4 As is clear from Table 4, if the pH is 6.0 or more and 9.0 or less, the bleach-fixing solution experiment No. 4-! 7 to 4-20 had good desilvering properties, recoloring properties, and liquid appearance without any problems, but Experiment No.
, 4-15.16, when P)I is low, the color becomes slightly coppery red, and the formation of iron thiocyanate is observed, and Experiment No.
, 4-21, it can be seen that when po becomes high, the desilvering property is affected. 5 Experiment No. 4-1~ in which thiosulfate or thiocyanate, which is outside the scope of the present invention, was used alone! 4
In the case of , it can be seen that there is a problem with desilvering property and/or recoloring property.

Example 5 The silver halide color photographic light-sensitive material used in Example 2 was subjected to live exposure using a camera, and then processed under the following conditions.

Processing process Processing time Processing temperature Replenishment amount Color development
3 minutes 15 seconds 38℃ 570g1 bleach fixing
3 minutes 15 seconds 38℃ 570 ■ Stabilization (3 tanks
x Kate) 1 minute 38 DEG C. 57 (HAL drying 1 minute 40 DEG -80 DEG C. (This amount of replenishment is the value per 1 m'' of light-sensitive material.) The composition of the processing liquid used in the above processing step is as follows.

Potassium Carbonate 30g Sodium Bicarbonate 2.5g Potassium Sulfite 3.0g Sodium Bromide
1.3g potassium iodide
1.2 g hydroxylamine sulfur IIk salt 2.5 g sodium chloride
o, eg4-7 minnow 3-methyl-N-ethyl-
Ni-(β-hydroxylethyl) aniline sulfate 4.5g diethylenetriaminepentaacetic acid 30g potassium hydroxide 1.2g Add water to make 1 liter,
PH10,0 using potassium hydroxide or 20% sulfuric acid
Adjust to 0.

Potassium carbonate 35g Sodium bicarbonate 3g Potassium sulfite
5g sodium bromide
0.5g hydroxylamine sulfate
3.584-amino-3-methyl-ethyl-
N (β-hydroxylethyl) aniline sulfate 6.0 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and adjust to pH 10.12 using potassium hydroxide or 20% sulfuric acid.
Adjust to.

Bleaching solution Bleached organic acid ferric ammonium salt (listed in Table 5) 0.35 mol Fixer (listed in Table 5) 2.5 mol ammonium sulfite (40% solution) 30 mJ
1 Ammonium ethylenediaminetetraacetate 2.0g5-
Amino-1,3,4-thiadiazole-2-thiol
Add 0.5 g of water and adjust the pH to 7.5 with aqueous ammonia or glacial acetic acid.

The auxiliary running process was continued until the bleach-fix tank was replenished with three times the capacity of the bleach-fix replenisher. However, 1
The daily running processing amount was such that the amount of liquid replenished to the tank capacity was 0.1 (referred to as 0, IR).

After the processing, the exposed photosensitive material was processed and evaluated in the same manner as in Example 2.

The results are shown in Table 5.

Table 5 As is clear from Table 5, the bleach-fix solution of the present invention (Experiment No.
, 5-6) were found to have good desilvering properties and good recoloring properties in running experiments.

Example 6 Bleach-fix solution 5-4, 5-5 and 5-6 in Example 5
The same evaluation as in Example 5 was performed except that the amount of bleach-fix solution replenished was changed as shown in Table 6.

The results are shown in Table 6.

Table 6: Amount of replenishment per 100 cm of wood photosensitive material As is clear from Figure 6, when the amount of bleach-fix replenishment is lowered, there is almost no effect on desilvering properties or recoloring properties, and low replenishment is possible. It turns out that it is quite possible.

On the other hand, when thiosulfate or thiocyanate is used alone as a fixing agent, desilvering and recoloring properties deteriorate due to low replenishment.
It can be seen that there is a significant difference from the present invention.

Example 7 A multilayer color reversal photosensitive material was prepared by sequentially coating two layers having the following compositions on a subbed triacetyl cellulose film support from the support side. The amount of each component applied is g/n
Indicated by f.

However, for silver halide, coating l calculated in terms of silver
Indicated by

AT layer (antihalation layer) Ultraviolet absorber U-10,3 Ultraviolet absorber U-20,4 High boiling point solvent 0-1 1.0 Black colloidal steel 0.24 Gelatin
2°O No. 21J (intermediate layer) 2.5-sheet octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 Gelatin 1.0 Third layer (low sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1,5
-2) spectrally sensitized^gllllrl (Ag 14.0 mol%, average particle size 0.25 μm) 0.5
Coupler C-10,3 High boiling point solvent 0-2 0.6 Gelatin 1.3 4th layer (high sensitivity red-sensitive silver halide emulsion layer) Red sensitizing dye (S-1,5
-2) spectrally sensitized^gBrl (Agl 2.5 mol%, average particle size 0.8 JLm)
0.8 Coupler C-11,0 High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer (intermediate layer) 2.5-di-t-octylhydroquinone 0.1 High boiling point solvent 0-1 0. 2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) Green sensitizing dye (S-3,5
-4) Spectrally sensitized AgBr [ (Ag 13.5 mol%, average particle size 0.25 μm) 0.8
Power Puller M-10,15 Power Puller M-20,04 High boiling point solvent 0-3 0.5 Gelatin 1.4 7th M (high sensitivity green-sensitive halogenated emulsion layer) Green sensitizing dye (S-3,5-
4) spectrally sensitized^girl (Agl 2.5 mol%, average particle size 0.8 final w) 0.9
Chikara Puller M-10,58 Chikara Puller M-20,12 High boiling point solvent 0-3 1.0 Gelatin 1.5 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Colorful colloid Silver 0.1 Gelatin 0.92.5-di-t
-Octylhydroquinone 0.1 High boiling point solvent 0-1
0.2 10th JiJ (low sensitivity blue-sensitive silver halide emulsion layer) AzBrl spectrally sensitized with blue sensitizing dye (S-5) (All 2.5 mol%, average grain size 0.35 #L11
) 0.8 Coupler Y -11,4 High boiling point solvent 0-3 0.8 Gelatin 1.3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S-5)
^gBrl (All 2.5 mol%, average particle size 0.8 pm) spectrally sensitized by
0.9 Coupler Y-13,5 High boiling point solvent 0-3 1.4 Gelatin 2.l 12th R: 1st
Protective layer UV absorber U-10,3 UV absorber U-20,4 2,5-sheet octylhydroquinone 0.1 High boiling point solvent 0-3 0.8 Gelatin
1.2 Thirteenth layer: second protective layer Non-photosensitive fine-grain silver halide emulsion made of silver iodobromide with an average grain size (r) of 0.08 gm and containing 1 mol% of silver iodide.
0.3 polymethyl methacrylate particles (1.5 #L diameter) O, OS
Surfactant 5A-10,004 Gelatin 0°7 In addition to the above composition, gelatin hardening agent H-1 and a surfactant were added to each layer.

UV absorber U UV absorber U 3 Sensitizing dye S ・N(C, Il,).

Coupler 0I+ Coupler Q Coupler M Gelatin hardening agent 11-1 Na Surfactant SΔ NaO+5 CIICOOCI+, (CF, CF! MlCIlyCO
OCII*(CF*CP*)-11C, 11°C, Il, t White light (5
50G'K) Knee r, 1/125 second exposure was performed. However, the exposure amount was lOc, X, s.

After exposure, the following development treatment was performed.

Processing process Processing time Processing temperature First development
6 minutes 38℃ water washing 2//
〃Reversal 2〃
〃Color development (3///
/Tone vi2 tt //Bleach, constant and young 3 tt ttWater wash
41/〃 Stable l〃 Dry at room temperature
The composition of the treatment liquid used in the drying step is as follows.

First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (l hydrate) Tophenyl-4-methyl-reef-hydroxymethyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (O,tX solution) Add water to make IJI.

Reversed violet Nitrilotrimethylenephosphonic acid 6 sodium salt Stannous chloride (dihydrate salt) P-7 minophenol Sodium hydroxide glacial acetic acid Add water to make a liquid.

Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) Potassium bromide g 2.58 1.2g mi g g O, Ig g wa 5 Maro potassium iodide (0,1! solution) 90 servings Sodium hydroxide 3g Citrazic acid
1.5g Toethyrut β-methanesulfonamidoethyl-3-methyl-4-aminoaniline-
1 g of sulfate Ill 2. Add 2-ethylenedithiodietano water to make Ill.

Okitoyo edition sodium sulfite Sodium ethylenediaminetetraacetate thioglycerin glacial acetic acid Add water and 1! Let it be L.

i blood test 1 shame Bleach-fix solution of Example 2 Definitely shy Formalin (37!i amount%) Konidax (Konica!1) 2g Rium (dihydrate salt) g 0.4m1 Three doses 5 Peng! 5m emperor Add water to make one sentence.

After the treatment, the same evaluation as in Example 2 was performed, and results similar to those in Example 2 were obtained.

Example 8 Polyethylene on one side of paper support and 1st F on the other side! Each layer having the structure shown below was coated on a support whose side was laminated with polyethylene containing titanium oxide to prepare a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows.

1st layer coating liquid yellow coupler (Y-1) 28.7g, dye image stabilizer (ST-1) IO, og, (ST-2) 8
．． 87g, additive (HQ-1) 0.8? , was dissolved in 8.87 g of high boiling point organic solvent ([1NP) by adding 60% of ethyl acetate, and this solution was mixed with 20% surfactant (SIJ-
1) 10% gelatin aqueous solution containing 7 lumps 220
ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 810 g) prepared under the following conditions to prepare a first layer coating solution.

The t52 layer to 7M coating liquids were also prepared in the same manner as the first layer coating liquid.

-1 C-1 T T-2 U V-2 DOP Diocdyl phthalate 1) I I) P Diisodenol phthalate 1-PVI Polyvinylpyrrolidone Q 11 U T I -1 I T-3 OC, l+.

S'r-5 still, as a hardening agent Below H- 1 was used.

- [Preparation method of blue-sensitive silver halide emulsion] The following (solution A) and (solution B) were controlled to pAg -6.5, pH -10 during 1000ml of a 2% gelatin aqueous solution kept at 40°C. The following (solution C) and (
1 while controlling solution D) to pAg-7.3, pH-5.5.
They were added simultaneously over 80 minutes.

At this time, pAg is controlled according to Japanese Patent Application Laid-Open No. 59-45431.
ρ11 was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Liquid A) Sodium chloride 1.42g Potassium bromide 0.0: Add Ig wood
200-view (B liquid) Add nitric acid ## Jog wood
200 ■ sentences (Liquid C) Sodium chloride 102.7g Potassium bromide 1.0g Add water
600 papers (D liquid) Add nitric acid #300g wood
After the addition of fi00, a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and 2 of sulfur magnesium were added.
After desalting using a 0% aqueous solution, it is mixed with a gelatin aqueous solution to form a layer with an average particle size of 0385μ and a coefficient of variation (σ/r
) = 0.07, a monodisperse cubic emulsion EMP-1 with a steel chloride content of 99.5 mol % was obtained.

The above emulsion EMP-1 was prepared at 50"C using the following compound.
A blue-sensitive silver halide emulsion (
Sodium thiosulfate 0.8 mg 1 mol^g
X Chloroauric acid
0.5 fist 87 mol AgX stabilizer SR-56X +0
-'eh/lh AgX sensitized color $ D -14,3X
10-'l/EA AgXD -40,7X 10
-'is/Mos AgX [Method for preparing green-sensitive silver halide emulsion] Addition time of (Liquid A) and (Liquid B) and (Liquid C)
The procedure was the same as ENP-1 except that the addition time of (Liquid D) was changed, and the average particle size was 0.43fiLm and the coefficient of variation (σ
/r) = 0.08, silver chloride content 99.5 mol%
A monodisperse cubic emulsion εNP-2 was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
Green-sensitive silver halide emulsion (EmB) after separation chemical ripening
I got 1.

Sodium thiosulfate 1.5 g/is A
gχ Chlorauric acid 1.0 mg 1 mol 1 mol Stabilizer SB -56X 10-'vs/es A
gX sensitizing dye D -24X 10-4 mol/mo, A
gX [Preparation method of red-sensitive silver halide emulsion] Same as EIIIP-1 except for changing the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D). average j
1 diameter 0.50gm, coefficient of variation (σ/r) = 0. O
ff, a monodispersed cubic emulsion [1'-3] having a steel chloride content of 99.5 mol % was obtained.

For EMP-3, use the following compound at 60°C! lO
Red-sensitive silver halide emulsion (EmC) after separation chemical ripening
I got it.

So-lium thiosulfate 1.8 mg 1 mol^
gX gold chloride@
2. Omg/l to g x stabilizer SR-
56x 10-'mol 1 mol AgX sensitizing dye D
-31, (lx 10-'t/f4 AgX) This sample was exposed to light according to a conventional method and then processed using the following processing steps and processing solution.

Processing step (1) Color development 9 35.0±0.3℃ (5 seconds (2) Bleach-fixing 35.0±0.5℃ 20 seconds (3) Stable (3 tank h skate) 30-34℃
90 seconds (0 drying 80℃~80
℃ 30 seconds moxibustion Triethanolamine 10g ethylene glycol! gN,N-diethylhydroxylamine 3.6ghydrazinodibutyric acid
5.0g potassium bromide
20-g1U potassium
2.5g diethylenetriaminepentaacetic acid lysate g Potassium sulfite 5. OX 10-4M Color developing agent (3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-7niline sulfate) 5.5g Potassium carbonate
258 Potassium bicarbonate
Add 5 g of water to bring the total volume to 1 liter, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

Triethanolamine 14゜0g ethylene glycol 8. OgN, N-
Diethylhydroxylamine 5g Hydrazinodiacetic acid 7.58 Potassium Bromide
81 potassium chloride
0.3g diethylenetriaminepentaacetic acid
7.5g potassium sulfite? ,
OX 10-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate) 8g Potassium carbonate 30g Potassium bicarbonate 1g Add water and crush completely. Adjust to 1gL and adjust pH to 10 with potassium hydroxide or sulfuric acid.
,40.

Bleaching solution and bleaching solution Jam ferric ammonium salt (Table 7 &)
0.35 mol ammonium thiosulfate
1.25tA ammonium thiocyanate
1.25 mol ammonium sulfite (40% solution)
30tl ammonium ethylenediaminetetraacetate 2.0g5-amino-1,3,4-thiadiazole-
Add 2-thiol 0.5g water,
Adjust the LQ to po 7.5 using aqueous ammonia or glacial acetic acid.

Firebox 1 Noro d1 Photoresponse Orthophenylphenol 0.1g Uvitex (manufactured by Ciba Geigy) 1.0g Zn5O
r7HzOQ, 1g ammonium sulfite (40% solution) 5.0si
l-Hydroxyethylidene-1,1-3,0g diphosphonic acid (60% solution) Ethylenediaminetetraacetic acid 1.5g Adjust to pH 7.8 with aqueous ammonia or sulfuric acid, and make up to 1 with water.

Running processing was performed using the prepared color paper and processing solution.

In the running process, the automatic processor is filled with the above-mentioned color developing tank liquid, as well as the bleach-fixing tank liquid and the stabilizing tank liquid, and the above-mentioned color developing replenisher is added every 3 minutes while processing the color paper sample. The bleach-fix replenisher and stable replenisher were replenished through a metering pump.

The amount of replenishment to the color development tank is 10 colors of color paper.
1.0 sJi per 0 cm, the amount of bleach-fixing replenisher to be refilled to the bleach-fixing tank was 2.2 grams per 100 cryi', and the amount of replenishing to the stabilizing tank was 2.5 ml of stable replenisher per 100 cm'.

The running treatment was carried out continuously at 0.05 R per mouth until the amount of bleach-fix tank solution replenished into the bleach-fix tank solution became three times the volume of the bleach-fix tank solution. Note that IR means that the bleach-fixing replenisher is replenished to the capacity of the bleach-fixing tank.

After continuous processing.

The same evaluation as in Example 2 was carried out. Ta.

The results are shown in Table 7.

Table 7 Maximum permeation density after main treatment - Maximum permeation temperature before treatment As is clear from the results in Table 7, the same results as in Example 2 were obtained.

This shows that at least it is possible to use the same bleach-fix solution for color negative film and color paper.

Claims (1)

Scope of Claims (1) In a bleach-fix solution for silver halide color photographic light-sensitive materials containing a ferric complex salt of diethylenetriaminepentaacetic acid as a bleaching agent, thiosulfuric acid is added per liter of the bleach-fix solution as a fixing agent of the bleach-fix solution. containing at least 1.0 mole of salt;
A bleach-fixing solution for silver halide color photographic materials, characterized in that it contains at least 0.5 mole of thiocyanate. (2) The bleach-fix solution for silver halide color photographic materials according to claim 1, wherein the bleach-fix solution contains at least 0.75 mol of thiocyanate per liter of the bleach-fix solution. (3) A method for processing a silver halide color photographic material, in which the silver halide color photographic material is subjected to at least a color development treatment step and a bleach-fix treatment step after imagewise exposure, the bleach used in the bleach-fix treatment step. The fixing solution contains as a bleaching agent a ferric complex salt of diethylenetriaminepentaacetic acid, and as a fixing agent at least 1.0 mol of thiosulfate and at least 0.0 mol of thiocyanate per liter of bleach-fixing solution.
A method for processing a color photographic material containing silver halide in an amount of 5 mol. (4) The method for processing a silver halide color photographic material according to claim 3, wherein the bleach-fix solution contains at least 0.75 mol of thiocyanate per liter of the bleach-fix solution. (5) The method for processing a silver halide color photographic light-sensitive material according to claim 3 or 4, wherein the amount of replenishment of the bleach-fixing solution is 7.0 ml or less per 100 cm^2 of the silver halide color photographic light-sensitive material. .