JPH01558A - Processing solution for silver halide color photographic light-sensitive materials that improves color recovery defects and processing method using the processing solution - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a processing solution for silver halide color photographic light-sensitive materials and a processing method using the processing solution.
The present invention relates to a processing solution for a silver halide color photographic light-sensitive material that can be applied to a silver halide color photographic light-sensitive material containing a high silver content to suppress leucoization of a cyan dye and improve color restoration defects, and a processing method using the processing solution.

[Background of the Invention] Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In color development step 1, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image. In the next desilvering step, the silver produced in the color development step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion complexing agent, commonly called a fixing agent. Ru. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. , and even a combination of these baths.

In addition to the above-mentioned basic steps, actual development processing includes various auxiliary steps to maintain the photographic and physical quality of the image or to improve the storage stability of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.

Commonly used bleaching agents include red blood salt, dichromate, and ferric chloride.
Iron, aminopolycarboxylic acid ferric button salt, aminopolyphosphonic acid ferric complex salt, super IIi! i acid salts are known.

However, blush salts and dichromates have pollution problems associated with cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Furthermore, ferric chloride has problems in the production of iron hydroxide and staining during the subsequent washing process, which poses some practical problems. Persulfates have the disadvantage that their bleaching action is very weak and that they require a significantly long bleaching time. Regarding this, a method has been proposed to increase the bleaching effect by using a bleaching accelerator in combination, but persulfate itself is regulated as a dangerous substance under the Fire Service Act and requires appropriate storage measures, making it generally difficult to put it into practice. There are drawbacks.

On the other hand, aminopolycarboxylic acid ferric complex salts (typically ethylenecyaminthi-1-la-acetic acid ferric complex salts) have less of the pollution problems that the above-mentioned bleaching agents have, and also have storage problems. It is a bleaching agent that is currently in widespread practical use.

However, the bleaching edge of the ferric aminopolycarboxylic acid complex salt is not necessarily sufficient, and processing solutions using this as a bleaching agent cannot be used with low-sensitivity silver halide color photography based on silver chlorobromide emulsions. When bleaching or bleach-fixing the material, the desired purpose can be achieved; When processing color reversal photosensitive materials for photography and color negative photosensitive materials for photography using high-silver 1 emulsion, there are drawbacks such as poor desilvering, often poor recoloring, and a long time required for bleaching. It had

For example, when bleaching color negative photosensitive materials for photography using a ferric aminopolycarboxylic acid complex salt, a bleaching time of at least 4 minutes is required, and desilvering requires subsequent bleaching. It is necessary to process with a fixing solution for at least 3 minutes or more, and if you try to shorten the bleaching time, you will have the problem of poor desilvering and poor recoloring as described above, so you have no choice but to lengthen the bleaching time. There wasn't.

Therefore, it has been strongly desired to shorten the time required for such a long desilvering process.

Methods of increasing the desilvering performance by increasing the bleaching time are methods such as lowering the pH of the bleaching solution, increasing the concentration of the bleaching agent, and furthermore, U.S. Pat.
-95631, mercapto compounds described in 53-141623, compounds having disulfide bonds described in 53-95630, Japanese Patent Publication No. 53-985
Thiazolidine derivatives described in Publication No. 4, JP-A-53-94
A method is known in which a bleaching accelerator typified by the isodiourea derivative described in No. 927 is added to a bleaching solution or a prebath. However, the method of lowering the pH of the bleaching solution has the disadvantage that, even though the bleaching speed is improved, poor color recovery tends to occur.Even when the concentration of the bleaching agent is increased, large amounts cannot be added due to the problem of precipitation of iron complex salts. The same drawbacks are likely to occur. In addition, the method of adding a bleaching accelerator has the disadvantage that it tends to form an H-soluble silver complex with silver, has poor solubility, and even if it is used, the recoloring property is not sufficient.

Therefore, as mentioned above, the bleaching time had to be long.

As a means of speeding up the desilvering process, German patent 86
It is known to process with a bleach-fix solution containing a ferric aminopolycarboxylic acid complex salt described in 6.605@ and a thioate salt as a fixing agent in one bath.

However, in the above bleach-fix solution, the oxidizing power of the ferric aminopolycarboxylic acid complex salt is originally weak, and the coexisting preservative, Ig! Thio@ which is salt and fixative
Since the acid salt is a reducing agent, aminopolycarboxylic acid secondary
It has the effect of further weakening the oxidizing power of iron complex salts, and as a result, it not only reduces the desilvering performance (but also easily converts the cyan dye formed by color development into leuco dye, and develops the leuco dye. However, this method has a problem of poor color reproduction, which causes a serious deficiency in color reproduction.

The above phenomenon becomes even more noticeable over time when a photosensitive material is continuously processed over a long period of time.

As a result of repeated studies on the above-mentioned problems, the present inventors have found that the above-mentioned poor color restoration is caused by the use of aminopolycarboxylic acid ferric complex salts and aminopolyphosboxylic acids as bleaching agents in the bleach solution or bleach-fix solution in the desilvering process. This is a common problem when using ferric complex salts of aminopolycarboxylic acids or aminopolyphosphonic acids, especially when the ferric complex salts of aminopolycarboxylic acids or aminopolyphosphonic acids act as oxidizing agents, resulting in reduction of the aminopolycarboxylic acid itself. It has been found that the accumulation of ferrous salts (complex ions) of acids or aminopolyphosphonic acids in processing solutions or sensitive materials poses a particularly serious problem.

It has also been found that the accumulation of ferrous complex ions depends on the pH of the bleach solution or bleach-fix solution, and the higher the 1)H, the more likely the formation of ferrous complex ions occurs. Furthermore, the formation of ferrous complex ions is a phenomenon that occurs due to the decomposition of the ferric complex salt of aminopolycarboxylic acid or aminopolyphosphonic acid itself. The sulfite contained as an agent also reduces the ferric complex salt to produce ferrous chain ions.Also, by processing high-silver photosensitive materials, silver is oxidized and the ferric complex salt itself is reduced. It has been found that ferrous Bq ions are present at high concentrations in the coating film of photographic light-sensitive materials during processing as ferrous complex ions, and leucoize cyan dyes.

Poor color restoration due to leucoization of this cyan dye is caused by high sensitivity,
This was particularly noticeable in photographic materials with a high silver content type having a film thickness of 13 μm or more.

If the above ferrous complex ions accumulate in a bleach solution or bleach-fix solution at a high concentration, the ferrous complex ions in the photographic light-sensitive material coating produced by the bleaching reaction will significantly diffuse out of the coating. It is thought that this suppresses the production of leuco dye and increases the defective color recovery.

Generally, in order to oxidize the ferrous complex ions of the aminopolycarboxylic acid or aminopolyphosphonic acid and activate them to ferric complex ions, a method called aeration, in which air is blown into the treatment liquid to oxidize it, is well known. ing.

However, this method also oxidizes sulfurous acid, which is a preservative, so it is not dangerous if there is a relatively long interval between treatments and the renewal rate of the solution is high, such as when processing color paper.
When there is relatively little processing material, such as color negatives, the oxidation of the solution progresses too much, causing sulfurous acid, which is a preservative, to oxidize, decomposing thiophilic acid salts, precipitating sulfur (sulfide), and causing precipitation, which is a serious problem. There is a risk of causing

Therefore, there is a strong demand for a method that does not cause poor color recovery even if ferrous complex ions are present to some extent.

It is also known that the above-mentioned poor color restoration can be improved by increasing the pH of the bleach solution or bleach-fix solution. Increasing the pH of the solution not only weakens the bleaching blade, but also makes it easier for ammonium thiosulfate and ferric ammonium salts to volatilize, causing odor to pollute the environment. Liquid I
) H is not feasible.

Further, US Pat. No. 3,189,452 discloses a method in which a red blood salt bleaching solution is used after bleaching and fixing to oxidize a leuco dye and return it to a cyan dye.

However, the use of red blood salt has the above-mentioned pollution problems and has the disadvantage that it involves an extremely difficult red blood salt recovery operation for practical use.

Therefore, there is a strong demand for a treatment method that does not cause defective color restoration even if ferrous complex ions accumulate during long-term running.

[Objective of the Invention 1 Therefore, the first object of the present invention is to provide a color photographic material,
Provided is a processing solution for silver halide color photographic light-sensitive materials in which leucoization of cyan dyes is unlikely to occur even in the processing of silver halide color photographic materials having high film thickness and high sensitivity and high silver content, and a processing method using the processing solution. There is something to do. A second object of the present invention is to provide a method of color development for dyes that is easy in practice and causes no problems in terms of pollution prevention.

[Structure of the Invention] The above-mentioned object of the present invention is to develop a semi-exposed silver halide color photographic material and use it as a bleaching agent with the following general formula [
I] and a compound represented by the general formula [I[]. After color development processing of the exposed silver halide color photographic light-sensitive material is carried out using a processing solution for silver halide color photographic light-sensitive materials containing a buffering agent and at least 1. In the method for processing a silver halide color photographic light-sensitive material, the desilvering step 511! The treatment bath used for P contains a bleaching agent and a ferric salt of at least one compound selected from the compounds represented by the following general formulas [I] and [II], Later, it was discovered that this can be achieved by a method for processing silver halide color photographic materials, which involves processing in an alkaline bath containing a buffering agent and having a temperature of 11+-18.0 or more.

General formula [I] General formula [II] In the formula, L is an alkylene group, a cycloalkylene group, a phenylene group, -La -0-La -0-La- or -L
12-Ls-. Here Z is L12-R9L12
R9 R++ R++ L1 to L+3 each represent an alkylene group. R1~R
t+ each represents a hydrogen atom, a water vi group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts). However, at least two of R1-R4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R5-R7 is a carboxylic acid group (including salts thereof). salts) or phosphonic acid groups (
(including its salt).

As a further preferred embodiment, (1) the alkaline bath contains a chelating agent having a chelate stability constant (ffioaKMA) with iron ions of 6 or more; By containing a ferric acid complex salt and (1) containing an oxidizing agent in the alkaline bath, the above object can be achieved more efficiently.

[Content structure 1 of the invention] The present invention provides bleaching agents of the formula M] and the general formula [II
Desilvering using a ferric complex salt of at least one compound selected from the compounds represented by ' ] (hereinafter referred to as ferric complex salt of the compound of the present invention), followed by treatment in an alkaline bath at pH 8.04X By this, the ferrous complex ions of the compound of the present invention that are generated, adsorbed and accumulated in the gelatin coating of the silver halide color photographic light-sensitive material are desorbed and quickly diffused out of the gelatin coating system, By creating an alkaline atmosphere, the color development of the cyan dye is significantly accelerated and defects in color recovery are improved.

In the present invention, the desilvering treatment performed after the color development step may be any process as long as the ferric complex salt of the compound of the present invention is used as a bleaching agent, but a preferred example An example of a targeted desilvering process is as follows.

[1] Bleach-fix [21 bleach-fix] [3] bleach-bleach-fix [4] bleach-bleach-fix [5] bleacher-bleach-fix [61 fix-bleach-bleach-fix In the above desilvering step, Bleaching and bleaching windows @ treatment bath, 1
In the treatment solution having bleaching ability in No. 11, a ferric salt of the compound of the present invention is used as a bleaching agent.

The compound of the present decoy is at least one compound selected from the compounds represented by the following general formula [I]a'3 and general formula [11].

General formula [I] General formula ['1 [wherein, is an alkylene group, a cycloalkylene group, a phenylene group, -La -0-La -0-La- or -
Represents LsZ-19-. Here Z is L12-R5L12
-Rs R1+ R++ 11 to L+3 each represent an alkylene group. R1~R
++ represents a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salts), or a phosphonic acid group (including its salts), respectively. However, at least two of R1-R4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R5-R7 is a carboxylic acid group (including salts thereof). (including its salts) or a phosphonic acid group (including its salts). 1. The ferric complex salt of the compound of the present invention used in the treatment solution having bleaching ability of the present invention contains ferric ion (Fe 3 ”)
and the compound of the present invention.

Typical specific examples of the compounds of the present invention are shown below A-1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid dinatrilam salt A-3 Ethylenediaminetetraacetic acid diammonium salt A-4 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt A- 5 Ethylenediaminetetraacetic acid tetrapotassium salt A-6 Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid trisodium salt A-8 Diethylenetriaminepentaacetic acid ammonium salt A-9 Diethylenetriaminepentaacetic acid pentasodium salt 8-10 Ethylenediamine-N- (β-oxyethyl)
-N, N', N' -Triacetic acid A-11 ethylenediamine-N-(β-oxyethyl)-N, N', N'
4-triacetic acid trisodium salt A-12 ethylenediamine-N-(β-oxyethyl)
-N, N', N' -Triacetic acid 1-diammonium salt A-13 Propylene cyamine diacetate 1-ammonium salt A-14 Propylene diamine tetraacetate 1-diammonium salt A-15 Nitrilotriacetic acid A-16 Nitrilotriacetic acid To trisodium salt -17 Cyclohexanediaminetetraacetic acid A-18 Cyclohexanediaminetetraacetic acid disodium salt A-19 Iminodiacetic acid A-20 Dihydroxyethylglycine A-21 Ethyl ether diamine tetraacetic acid A-22 Glycol ether diamine tetraacetic acid A-23 Ethylenediaminetetrapropionic acid A-24
1,2-Diaminopropane tetraacetic acid ammonium salt A-25 1,2-diaminopropane tetraacetic acid sodium salt A-26 Hydroxyiminodiacetic acid ammonium salt A-27 Hydroxyiminodiacetic acid sodium salt A-28
Triethylenetetraminehexaacetic acid A-291,3-diaminopropan-2-ol-tetraacetic acid A-30Phenylenediaminetetraacetic acid A-31Nitrilotripropionic acid A-32Ethylenediaminetetramethylenephosphonic acid A-33Diethylenetriaminepentamethylenephosphonic acid - A-34 Cyclohesanediamine tetramethylene phosphonic acid A-35 Nitrilotrimethylene phosphonic acid A-36 Iminodimethylene phosphonic acid Among these compounds, aminopolycarboxylic acids are preferred, especially A-1 to A-3, A-3 -8, A-13, 8-14, 8-17 to A-19, A-22, 8-24 to A
-27 is preferred.

The ferric complex salt of the compound of the present invention used in the present invention may be used in the form of a complex salt, or a ferric salt such as rlII
Ferric ion complex salts may be formed in solution using the compounds of the present invention with ferric iron, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the like. When used in the form of complex salts, one type of complex salt may be used, or two types of complex salts may be used.
More than one type of complex salt may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and the compound of the present invention,
One or more types of iron salts may be used. Furthermore, one type or two or more types of compounds of the present invention may be used. Moreover, in any case, the compound of the present invention may be used in excess of the amount required to form the ferric ion complex.

Further, the bleaching solution containing the ferric ion complex described above may contain a complex salt of a metal ion other than iron, such as cobalt, copper, or nickel.

In the liquid having bleaching ability of the present invention, the ferric complex salt of the compound of the present invention is contained in an amount of 0.0% per 12 liquid having bleaching ability.
The amount is preferably 0.5 to 2 mol, more preferably 0.1 to 1.0 mol.
0 mol, particularly preferably in the range of 0.2 to 0.6 mol.

In the desilvering process of the present invention, when a bleaching solution is used, in addition to the ferric salt of the compound of the present invention as the bleaching agent, the bleaching solution contains iPI, FlF + sand, metaboric acid, sodium hydroxide, hydroxide. pH consisting of various salts such as potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
! ! Buffers, halogen compounds such as potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. Can be normally used in bleaching solutions may optionally contain known additives.

The pH of the bleaching solution of the present invention is preferably in the range of 4.0 to 8.0, more preferably 5.0 to 6.5.

When a bleach-fix solution is used in the desilvering step of the present invention, the bleach-fix solution contains, in addition to compounds that can be added to the bleach solution, J: halogenated silver halide fixing agents used in normal fixing processing. Compounds that react with silver to form water-soluble complexes, such as thiosulfates such as potassium thiosulfate, sodium thio[0, ammonium thio'fAW, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate. , thiourea, thioether, high temperature bromide, iodide, etc. are used. These fixing agents can be used in an amount that can dissolve 5 g/2 or more, preferably 50 (+/y or more, more preferably 70 a/Q or more).

Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also, preservatives such as hydroxylamine, hydrazine, aMf:j, isomeric bisulfite, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, and oxycarboxylic acid. , organic chelating agents such as polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids, or stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and methanol. , dimethylformamide, dimethylsulfoxide, and other organic solvents.

The pH of the bleach-fix solution of the present invention is preferably in the range of 3.0 to 9.8, more preferably 5.6 to 8.5, particularly preferably 6.0 to 8.3.

When using a fixing solution in the desilvering step of the present invention, the fixing solution includes:
Thio Ili! mentioned in the bleach-fix solution above as a silver halide fixer! ! A fixing agent such as an acid salt or a thiocyanate is contained.

In addition, as preservatives for fixing agents, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, various pHl 1 buffers mentioned in bleaching solutions, and halogen compounds can be used. It may contain known additives commonly used in fixers.

The pH of the fixer is preferably in the range of 5.0 to 8.5, more preferably 6.0 to 8.0.

In the above desilvering process, the used bleach bath overflow solution flows out from the bleach bath as a result of adding bleach replenisher to the bleach bath, and the used fixer flows out from the fixer bath as a result of adding fixer replenisher to the fixing bath. A respective part or all of the bath overflow liquid can be introduced into the bleach-fixing bath. In that case, the overflow liquid from both the bleaching and constant cleaning baths can be effectively reused, without adversely affecting the desilvering performance.
It is also possible to reduce the total amount of replenisher, which is a preferred embodiment.

In the present invention, the desilvered silver halide color photographic light-sensitive material is treated with I) an alkaline bath having a temperature of 88.0 or higher and containing a buffer. When processing in an alkaline bath, it is of course necessary to carry out continuous alkaline bath treatment after desilvering treatment, as well as water washing, rinsing, and further water washing as described in JP-A No. 57-8543 etc. A stabilization treatment as an alternative to washing may be performed to extremely reduce the amount of water.

Considering costs and the like, it is preferable to carry out continuous alkaline bath treatment after desilvering treatment.

Hereinafter, the alkaline treatment solution of the present invention having a pH of 8.0 or more and containing a buffer (hereinafter simply referred to as the alkaline bath of the present invention)
I will explain about it.

The buffer used in the alkaline bath of the present invention is pl-18
, any compound can be used as long as it has a stable lIz'fE effect in an aqueous solution of 0 or more, but specific examples include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, Ammonium carbonate, 11Fjll, borax, inorganic salts such as sodium metatilate, sodium phosphate, potassium phosphate, sodium 1'g4 acid, amines such as ethanolamine, ethylenediamine, methylamine, trimethylamine, propylamine, hydroxyproline, O Ishin,
Examples include amino acids such as glycine, alanine, aspartic acid, and γ-aminobutylacetic acid, and various organic compounds such as sulfosalicylic acid, piperazine, and guanidine, and these can be used alone or in combination.

As the buffering agent used in the present invention, considering the cost, the effect of improving the color recovery defect of the present invention, the DH maintenance effect during long-term continuous use, and the adverse effect on other photographic performance, sodium carbonate, potassium carbonate, bicarbonate, etc. potassium, boric acid,
Borax, sodium metaborate, sodium phosphate, potassium phosphate, monobasic phosphate, sulfosalicylic acid, and the like are preferably used.

The amount of the buffer used in the alkaline bath of the present invention is 1))=1 of the alkaline bath! ! Shocking agents vary greatly depending on the type of buffer, and if too much is used, the image of the processed photosensitive material will be smudged, and if a small amount is used, problems such as poor buffering effect will occur, so the buffering agent is determined by the conditions of the alkaline bath. However, as a guide, it is preferable to use in the range of 0.2 to 50 g per 1 alkaline bath.
More preferably, it is 0.5 to 30 g.

In the present invention, alkaline bath treatment can be used in one bath or in multiple baths without any problem, but preferably in one to two baths.

In addition, the alkaline bath of the present invention may be used in the same manner as other conventionally known photographic processing baths, and specifically, a sufficient amount of replenisher may be supplied; It is preferable to minimize selection.

The amount of photographic processing solution carried from the pre-bath to the alkaline bath varies depending on the type of photosensitive material, the conveyance speed of the automatic processor, the conveyance method, the method of squeezing the surface of the photosensitive material, etc., but in the present invention, Based on the unit area of 2514/v2~150tN
/ v' is preferable, and the effect of the present invention on these introduced insects is more pronounced T: Al M Full Ha 501Q
/f ~3. There are Otl/f(7)I surroundings, and the most effective supplements are 1001β/f to 950112/v”
within the range of

By containing a chelating agent having a chelate stability constant (j!O(IKMA)) of 6 or more with iron ions in the alkaline bath of the present invention, the effects of the present invention, specifically, poor color recovery can be improved. Improvements can be achieved more effectively.

It also has the effect of preventing hydroxide formation of soluble iron salts brought into the alkaline bath.

Here, the chelate stability constants are L and G.

5ill, en, A. E. Martell, "3 tabil 1tyConstants
of Metal-ion Complexes
”.

The Chemical 3ociety,
London (1964), S. Chabe
rek, by A. E. Martell.

“Qrganic 3equestering A
gents'', a constant commonly known by Wiley (1959) and others.

In the present invention, examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelates, organic aminopolycarboxylic acids, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. It will be done. Note that the iron ion mentioned above refers to ferric ion (Fe
3 + ) and ferrous ions (Fe 2 + ).

In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 6 or more with iron ions include the following compounds, but are not limited thereto. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenibrobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid. Acetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilo-1-rimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1 .1-
Diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1
-Phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium birophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, and particularly preferred are diaminopropane-tetraacetic acid, diethylenetriamine-pentate These are acetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, ethylenediaminetetraacetic acid, and their salts.

The above-mentioned chelating agent used in the present invention is used in an amount of 0.01 to 50 g, preferably 0.01 to 50 g per 11 alkaline baths.
．． Good results are obtained in the range of 05 to 20a.

In the present invention, it is extremely preferable for the alkaline bath to contain a complex salt of the chelating agent and iron ions, that is, an iron complex salt, from the viewpoint of improving color restoration defects. Particularly preferred compounds include ferric sodium salt of ethylenediaminetetraacetic acid, ferric sodium salt of diethylenetriaminepentaacetic acid, ferric sodium salt of propylenediaminetetraacetic acid, and ferric sodium salt of 1゜2-diaminopropanetetraacetic acid. , the amount added is 0 per 12 alkaline baths.
．． 5 to 30 (I), particularly preferably 2 to 15 g.

In the present invention, the overflow liquid of the liquid having bleaching ability is poured into an alkaline liquid, and the ferric aminopolycarboxylic acid complex salt is present at a concentration of I x 10' mol or more per alkaline bath 12, so that the roughness can be restored. Color defects can be effectively prevented.

Further, as an oxidizing agent in the alkaline bath of the present invention, for example, hydrogen peroxide, sodium percarbonate, sodium perborate, potassium persulfate, ammonium persulfate, sodium chlorate, sodium hypochlorite, potassium bromate, ammonium bromate, By containing sodium bromate or the like, poor color recovery can be effectively prevented. The amount of the oxidizing agent added is preferably 0.01 g to 30 (J/l).

In the treatment method of the present invention, the above-mentioned alkaline bath treatment may be completed, and further treatment may be performed with water washing treatment or with a stabilizing treatment liquid that does not substantially use washing water.

In the present invention, the latter stabilization treatment that substantially does not use washing water is preferred as the treatment after the alkaline bath.

The stabilizer solution may basically consist of only water, but various compounds may also be added. Compounds that can preferably be used in the present invention include formalin, surfactants, ammonium salts, chelating agents, and metal salts. be.

A fungicide may be used in the alkaline bath or stabilizing solution of the present invention, if necessary. The antifungal agents used include hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds,
Carbamate compounds, morpholine compounds, quaternary phosphonium compounds, quaternary ammonium compounds, urea compounds, isoxazole compounds, propatoolamine compounds, sulfamide derivatives, amino acid compounds,
These are triazine compounds and benzotriazole compounds.

In the processing method of the present invention, in addition to the steps such as color development, desilvering treatment, and alkaline bath treatment according to the present invention, various steps such as hardening, neutralization, black and white development, reversal, and small amount washing with water are performed as necessary. Auxiliary steps may be added.

There are basically no restrictions on the type of silver halide color back-sensitive materials that can be applied to the processing method of the present invention, but those that are particularly effective for use in the present invention include at least one silver halide emulsion layer. This is a highly sensitive photographic material having silver halide grains containing silver iodide in an amount of 0.5 mol % or more, preferably in the range of 3 to 10 mol %. Further, the total dry film thickness of all the photographic constituent layers on the side having the silver halide emulsion layer on the support is 13 μm or more, preferably 15 μm to 28 μm,
More preferably, it is a photosensitive material having a diameter of 17 μm to 24 μm, and the amount of silver coated on the support is 20 mg/10 μm.
0cf or more, preferably 30μm1g/100C12~
80mg/100Cf, preferably 40111 (
1/100Ct' ~ 7011 (J/100Ct')
High i! There are ffi photosensitive materials.

The silver halide emulsion of the silver halide color photographic light-sensitive material applicable to the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened or may contain a plasticizer or a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

Supports include 0 paper laminated with polyethylene, polyethylene terephthalate film, baryta paper,
Cellulose triacetate etc. can be used.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, a black colloidal silver antihalation layer, a red-sensitive colloidal silver antihalation layer, and a red light-sensitive layer were coated from the support with various auxiliary layers interposed. a green-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer is disposed on the outermost side of the blue-sensitive silver halide emulsion layer. did. However, the amount of silver coated is 60 so/
100 cf, and the dry film thickness was 25 μm.

Layer 1: A dispersion of black colloid @0.8[1, which exhibits high absorption to light in the wavelength range of 400 to 700 nm, is prepared by reducing silver nitrate with hydroquinone as a reducing agent and 3 g of gelatin to form an antihalation layer. Painted.

112...Medium WAIW consisting of gelatin.

Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (A
gI: 7 mol%), 1.6 g of gelatin and 08
0 g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxylphenoxy)butyl]-2-naphthamide (hereinafter referred to as cyan coupler (C-1))
,0. 028! ] of 1-hydroxy-4-[4-(1
-Hydroxy-8-acetamido-3,6-disulfo-
2-naphthylazo)phenoxy]-N-[δ-(2,4
-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CG)
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved therein.

Layer 4: 1.1 g of red-sensitive silver iodobromide emulsion (A
gl: 6 mol%), 1.2 g of gelatin and 0.23
! ] cyan coupler (C-1), 0,020 (0159 in which colored cyan coupler (CC-1) of J was dissolved
A highly sensitive red-sensitive silver halide emulsion layer containing TCP.

Layer 5...0.07 (l of 2,5-di[-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1))
An intermediate layer containing 0.04 dibutyl phthalate (hereinafter referred to as DBP) dissolved in 1.2 g of gelatin.

@6...1.69 low-sensitivity green-sensitive silver iodobromide emulsion (A
g f: 12 mol %), 1.7 g of gelatin and 0.7 g of gelatin.
30 (l of 1-(2,4,6-1-lichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler ( M-1>), 0, 20(]
]4,4-methylenebis-11-2,4.6-dolychlorophenyl)-3-[3=(2,4-di[-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler) (referred to as (M-2))
, 0.066 (I of 1-(2゜4.6-dolichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5
- Pyrazolone (hereinafter referred to as colored magenta coupler (CM)
-1>) dissolved in three types of couplers, 0, 3(l
A low-sensitivity green-sensitive silver halide emulsion layer containing TCP.

Layer 7: 1.5 g of green-sensitive silver iodobromide emulsion (A
gl; 10 mol%), 1.9 g of gelatin and 0.0
93+II magenta coupler (M-1), 0.094
(0 in which 1 of magenta coupler (M-2), 0.049++ of colored magenta coupler (CM-1) was dissolved,
High-sensitivity green-sensitive silver halide emulsion layer containing 12(l) of TCP.

Layer 8...Yellow filter layer containing 0.2 g yellow colloidal silver, 0.11 (l DIR and 2.11 J gelatin) dissolved in 0.2 g antifouling agent (HQ-1).

Layer 9: 0.95 fJ low-speed blue-sensitive silver iodobromide emulsion (A(II; 7 mol%), 1.9 g gelatin and 1
, 84 (l of α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1°2,4-triaziridinyl)]-]α-pivaloyl-2-chloro5[γ-(2,
4-di[-amylphenoxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1))
A low-speed blue-sensitive silver halide emulsion layer containing DBP of 0.93(1) dissolved in

Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (Aol: 6 mol%), 2.0g of gelatin and 0.46g of yellow coupler (Y-1) were dissolved.
, 23 (High-sensitivity blue-sensitive silver halide emulsion layer containing 1 DBP.

Layer 11...Second layer made of gelatin! layer.

Layer 12: first protective layer containing 2.3 g of gelatin.

This sample was cut into pieces, subjected to model exposure according to a conventional method, and processed using a piece processing device according to the following steps (hereinafter referred to as manual processing).

Processing process Processing temperature ('C) Number of tanks Processing time 1, color development 318 1 tank 3 minutes 15 seconds 2, bleach-fixing 37.8 1 tank 3 minutes 30 seconds (however,
l)H of the bleach-fix solution was as shown in Table 1 below. ) 3. Alkaline bath 30-34 2 baths 3 minutes 30 seconds (However, I)H of the alkaline bath was as shown in Cloth-1 below. 〉 4. Stable 30-34 1 tank 2 minutes 10 seconds 5, dry The following were used as the dry color developing solution, bleach-fix solution, alkaline bath solution, and stabilizing solution.

[Color developer] [Bleach-fix solution] The discharge was adjusted using L as shown in Table 1.

Furthermore, silver powder was added to reduce the ferric diammonium salt of ethylenediaminetetraacetate, and the pH was again adjusted to Table 1 so that 40>ferrous diammonium salt of ethylenediaminetetraacetate was produced.

[Alkaline bath solution] [Stabilizing solution] A photosensitive material sample was processed according to the above procedure, and the amount of residual bacteria silver (iM df) at the highest concentration in the processed sample was measured by fluorescent X-ray method. Furthermore, the cyan dye concentration was measured using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.), and using this value, the same sample was treated with a 3% blush salt solution at room temperature in a conventional manner. The color restoration rate was calculated by setting the cyan dye density after processing for 10 minutes to 100.

The results are summarized in Table-2.

] Below 5 margins -0, “; Table 2 As is clear from the results of Table 2, bleaching window @ 1 after treatment
Those treated with an alkaline bath of 1H8.0 or higher have a remarkable effect of improving desilvering properties and defective restoration of cyan dye.

Moreover, when looking at the relationship with the pH of the bleach-fix solution, it can be seen that favorable results are shown when the pHIfi of the bleach-fix solution is particularly 6 to 8. Further, the results show that the pH of the alkaline bath is preferably 9.0 or higher.

Example-2 The following alkaline bath was prepared.

[Alkaline bath solution] Example-1 as a bleach-fix solution using the above alkaline bath
The same experiment and evaluation as in Example-1 were conducted except that I) 86.5 was used.

Furthermore, regarding the alkaline bath, 5
After being stored at 0° C. for 5 days and 10 days, each sample was treated in the same manner as above using each storage alkaline bath, and deterioration after storage in the alkaline bath over time was observed.

The results are also shown in Table 3.

1 margin below; j ′-12I・3 Table 3 As is clear from the results in Table 3, in Experiment Nos. 2-2 to 2-13 using the alkaline bath of the present invention, all
Although the effect of improving the poor color recovery is remarkable even after the test, the comparative experiment No. 2-1 using an alkaline bath with a pH of less than 8.0 has a large defect in color recovery regardless of whether it is stored or not. Also, pH 10.0
In Comparative Experiment No. 2-14 using an alkaline bath without using a binding agent, the improvement effect on the color recovery rate was satisfactory immediately after the alkaline bath was prepared, but the color recovery rate deteriorated over time. It can be seen that this is insufficient and a stable photographic image cannot be obtained.

Example-3 Processing steps in Example-1, namely 10 color development, 2.
Bleach fixing, 3. Alkaline bath, 4. An experiment was conducted by replacing each of the stable treatment steps with the treatment step shown in Cloth-4 below.

Table-4-2 Among the processing solutions used in the above processing steps, the bleach-fix solution used in Example-1 J3 l1l-11) and 5 was used.
Similarly, IIHlo, 0 Shino was used as the alkaline bath.

Further, the following components other than the whitening solution and the fixing solution were the same as those in Example-1.

[Bleaching Solution] As in Example 1, silver powder was added to reduce the ferric diammonium salt of ethylenediaminetetraacetate so that the concentration of the ferrous diammonium salt of ethylenediaminetetraacetate was 400%.

[Fixer] An experiment similar to Example 1 was conducted except for the above processing steps,
The recoloring rate and desilvering properties were examined. The results are shown in Table-5.

As is clear from Table 5, it can be seen that even when the desilvering treatment is varied, poor color recovery is significantly improved by applying the alkaline bath treatment of the present invention.

Example-4 In Example-1 above, I)H of the bleach-fix solution was 6.5.
, the p)l of the alkaline bath was set to 10.0, and the aminopolycarboxylic acid or aminopolyphosphonic acid shown in Clothing-6 below was added in place of the ferric diammonium salt of ethylenediaminetetraacetate as the aminopolycarboxylic acid in the bleach-fix solution. An experiment was conducted in the same manner as in Example 1, except that the ferric complex salt was used at the concentrations shown in Table 6. The results are also shown in Table 6.

Table 6 As is clear from the results in Table 6, it can be seen that the effects of the present invention can be obtained even if the type and concentration of the bleach used in the bleach-fix solution are changed. Example 5 An experiment was conducted in the same manner as in Experiment No. 4-1 of Example 4, except that 10 (J) of the additives shown in Table 7 below were added to the alkaline bath 12.

The results are also shown in Table-7.

Table 7 Ferric sodium salt of diaminetetraacetate Lentriamineferric sodium salt of diaminetetraacetate Ferric sodium salt of hexanediaminetetraacetate Ferric sodium salt of hexanediaminetetraacetate 36% aqueous solution) Potassium thorium 3/2 H202 Sodium 1202 , when the alkaline bath contains a chelating agent having a stability constant of 6 or more with iron, and when the second compound of the present invention
It can be seen that when the iron complex salt is contained at a certain concentration or more, and when the oxidizing agent is further contained, the effect of improving color restoration defects according to the present invention is even more remarkable.

Example 6 In Example 1, except that the film thickness of the photosensitive material to be processed (only the gelatin thickness was changed) and coating silver m were changed to use the photosensitive material shown in Coating 8 below. Experiment N
The experiment was conducted in the same manner as in 0.1-24. However, for comparison, an experiment was conducted in which no alkaline bath was used. The results are also shown in Table-8.

Table 8 As is clear from the results in Table 8, the processing method of the present invention is not significantly affected by the film thickness of the photosensitive material or the amount of coated silver, and can provide a good effect of improving color regeneration defects. Film thickness 1
It is more than 3μ false. (When the film thickness is 13 μm or less, the defective color reproduction is small.) When the film thickness is 16 μm or more, a particularly large improvement result is obtained, and it can be seen that the larger the number of coated silver mines, the greater the improvement effect.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (2)

[Claims] (1) The exposed silver halide color photographic light-sensitive material is color developed and at least one compound selected from the following general formulas [I] and [II] is used as a bleaching agent.
An alkaline treatment liquid used after desilvering using a ferric complex salt of two compounds, the alkaline treatment liquid being p
A processing liquid for silver halide color photographic materials, characterized in that it has a H8.0 or higher and contains a buffering agent. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, L is an alkylene group, cycloalkylene group, phenylene group, L_8-O- L_3-O-L_3- or-
Represents L_9-Z-L_9-. Here, Z represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. L_1 to L_1_3 each represent an alkylene group. R
_1 to R_1_1 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R_1 to R_4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R_5 to R_7 is a carboxylic acid group (including salts thereof). (including its salts) or a phosphonic acid group (including its salts). ] (2) In a method for processing a silver halide color photographic light-sensitive material in which the exposed silver halide color photographic light-sensitive material is subjected to color development processing and then at least desilvering processing, the processing bath used for the desilvering processing may contain a bleaching agent. The following general formula [ I
] and a ferric complex salt of at least one compound selected from the compounds represented by the general formula [II], and after the desilvering treatment, is treated with an alkaline bath having a pH of 8.0 or more and containing a buffer. A method for processing a silver halide color photographic material, characterized in that: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, L is an alkylene group, cycloalkylene group, phenylene group, -L_8-O -L_8-O-L_8- or -L_9-Z-L_9-. Here, Z represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. L_1 to L_1_3 each represent an alkylene group. R
_1 to R_1_1 each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group (including its salt), or a phosphonic acid group (including its salt). However, at least two of R_1 to R_4 are carboxylic acid groups (including salts thereof) or phosphonic acid groups (including salts thereof), and at least one of R_5 to R_7 is a carboxylic acid group (including salts thereof). (including its salts) or a phosphonic acid group (including its salts). ]