JP2003202654A - Bleach-fixing concentrated composition for silver halide color photographic sensitive material and processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method and a bleach-fixing concentrated composition having performance to suppress sticking on transport rollers and drive gears in an automatic processing machine and swelling of rollers themselves, having concentrated one-part form and less liable to deterioration particularly even in an unsealed state and to therefore provide a processing method and a bleach-fixing concentrated composition that can be diluted and used in a replenishment tank as usual and can stably be used even in a system in which the concentrated composition is held in the concentrated form in an automatic processing machine in a mini-laboratory and the concentrated composition and replenishing water are separately replenished in replenishment. <P>SOLUTION: In the bleach-fixing concentrated composition for a silver halide photographic sensitive material containing at least 0.3-0.6 mol/L ferric complex salt of an aminopolycarboxylic acid (A) and a salt of an aminopolycarboxylic acid (B) not forming a complex salt, the molar concentration of the salt of the aminopolycarboxylic acid (B) is 0.01-2% of that of the ferric complex salt of the aminopolycarboxylic acid (A). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleach-fixing concentrated composition for silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials and light-sensitive materials) and a processing method using the same.
Specifically, it has the ability to suppress sticking on the transport roller and the drive gear in the automatic processor and swelling of the roller itself,
The present invention relates to a bleach-fixing concentrated composition for a light-sensitive material, which is in a concentrated 1-part form, and shows little deterioration even when opened, and a processing method using the same.

[0002]

2. Description of the Related Art For photographic processing, production centers are shifting from conventional central laboratories to so-called minilab stores.

The processing in the minilab is carried out by installing a developing processing device (generally called an automatic developing machine) capable of small size and rapid processing at each photo retail store.
The advantage is that the customer can receive the finished product at the place where the order is placed, and the time from ordering to receiving is greatly shortened. Further, the miniaturization of the automatic processor itself in the minilab has progressed, and it has become possible to install it in a place where it could not be installed conventionally. However, for example, there is a strong demand for further downsizing of the automatic processor in order to secure a space for displaying products even in a tenant store of a large-scale store, an underground sales floor of a department store, or even a retail store. Has become. In addition to the problem of the installation area, there are problems such as water supply for making photographic processing solutions and facilities for disposing and storing processing effluents are distant or insufficient. Improvement is required.

In a general photographic processing process including an automatic processor in a minilab, a processing solution is replenished with a prescribed amount of a replenishing solution depending on the processing amount of a light-sensitive material in order to maintain the activity of the processing solution or at regular intervals. Even in the automatic developing machine in the minilab, the replenishing solution stored in the replenishing tank is generally supplied to the processing tank by a supply means such as a pump. The replenishing solution in the replenishing tank is reduced by being replenished in the processing tank, and when a certain amount is reached, a concentrated composition for producing a new replenishing solution (so-called kit, replenishing solution kit, etc.). Is used to prepare a replenisher and the tank is replenished.

The replenisher kit can be in a concentrated form for downsizing, but in many cases, it is packaged in a plurality of parts to improve the storability, and each part is poured into a replenishing tank every time the replenisher is prepared. Then, a prescribed amount of dissolved water is added, and a predetermined amount of replenisher solution is obtained. Injecting from the opening of a plurality of parts and diluting by adding water must be performed in parallel with the work of performing the printing operation or interrupted, which is a troublesome work.

On the other hand, paying attention to the processing of the photosensitive material in the automatic processor in the minilab, the photosensitive material imagewise exposed in the automatic processor in the minilab is usually subjected to a color developing step, a bleaching step, a fixing step (or a bleach-fixing step). Process),
Although it is processed by washing with water or a stabilization process, it is generally transferred by a transfer roller or the like into a processing tank filled with various processing solutions and processed.

The space between each processing tank is introduced into the next processing tank while the transfer path is defined by the transition member. The final image is obtained by being processed by the above process and then dried by the drying process.

Under low processing conditions with a small amount of processing sensitizing material, the composition and concentration change due to oxidation and evaporation of water in the processing solution. Therefore, a processing replenisher or evaporation replenisher is added every time. Permeation into the processing rack or the conveyance system drive section due to the interface (inner wall of the processing tank), the transition member that comes into contact with the photosensitive material when passing through the photosensitive material, or the capillary phenomenon occurs, and finally the processing liquid is fixed due to drying.

Further, the roller member is deteriorated due to swelling or the influence of the components of the treatment liquid in the treatment liquid in which a high-concentration component is dissolved, and when the deterioration is severe, the roller surface may be deformed or cracked. is there.

When the processing liquid component is deposited, the driving performance itself may be affected in the driving part, and the surface of the photosensitive material may be damaged or contaminated if it is on the photosensitive material passage. .

Deformation of the roller affects the conveyance of the photosensitive material and causes not only jamming, but also precipitation on the uneven surface, which easily adheres to the surface of the photosensitive material. Also greatly affects the quality of the finished photo.

Further, the precipitation phenomenon at the interface of the treatment liquid occurs not only in the treatment tank but also in the treatment replenisher tank. This is especially noticeable when the replenisher to be retained has a high concentration.

It has been found that such a phenomenon as swelling or precipitation of the roller occurs frequently in the bleach-fixing step having a high concentration of components and its surroundings, and in view of the above handling, it is compact and easy to use, and It is desired to develop a bleach-fix replenisher that operates stably in terms of processing performance and does not impair print quality.

[0014] In the bleach-fix solution kit (concentrated composition), attempts have been made to make it into one part in order to improve the complexity of multiple parts. However, the bleach-fix solution contains a bleaching agent and a fixing agent, and is generally a fixing agent. It is known that the compound has a reducing property and the bleaching agent has an oxidizing property, and both react with each other to be inactivated. Therefore, a preservative such as sulfite is used, but the preservative is decomposed by storage. Even in the presence of a preservative, when concentrated to a high concentration, the two react with each other to a large extent, leading to inactivation.

For this reason, one part is known, but only one with a concentration to be used without dilution or with a limited range even if diluted is known. Although it is simple, the replenisher kit itself occupies a large space and is insufficient in terms of handling.

The one-part concentrated composition of the bleach-fix solution kit is disclosed in Japanese Patent Laid-Open No. 2000-98558 and the like, and attempts have been made to improve the stability in the kit state, but the storage stability is sufficient. However, the storability especially in the opened state was a problem.

It is necessary to dilute such a replenisher solution immediately after opening it to obtain a replenisher solution form. 1) A replenisher tank for holding the diluted replenisher solution is required for each type of treatment solution ( If the replenishment tank is large, the automatic processor itself will be large, and if it is small, the number of times the replenisher is adjusted will increase. Moreover, 2) the task of adding the specified amount of water required to dilute the concentrate still remains. Alternatively, it is possible to provide an automatic developing machine with a function of automatically diluting, but this also raises a problem that the size and cost of the automatic developing machine are promoted.

[0018]

In view of the above problems, the problem to be solved by the present invention is to improve the performance of suppressing the sticking on the conveying roller or the driving gear in the automatic processor and the swelling of the roller itself. The present invention provides a bleach-fixing concentrated composition for a light-sensitive material which has a concentrated 1-part form and exhibits little deterioration even when opened, and a processing method using the same. A bleach-fixing concentrated composition for a light-sensitive material which can be used and can be stably used even in a system in which it is kept in a concentrated form in an automatic processor in a minilab and separately replenished with a concentrated composition and replenishing water when replenishing. And a processing method using the same.

[0019]

The present invention for solving the above problems has the following constitution. 1. Bleach-fixing for silver halide photographic light-sensitive materials containing at least 0.3 to 0.6 mol / L of a ferric iron complex salt of aminopolycarboxylic acid (A) and a salt of aminopolycarboxylic acid (B) not forming a complex salt In the concentrate, the content mol concentration of the aminopolycarboxylic acid (B) salt is 0.01% or more and 2% or less of the content mol concentration of the ferric iron complex salt of the aminopolycarboxylic acid (A). A bleach-fixing concentrate composition for a light-sensitive material.

2. The aminopolycarboxylic acid (A) second
A compound in which the aminopolycarboxylic acid used for the iron complex salt is different from the aminopolycarboxylic acid (B), and the ferric iron complex stability constant of the aminopolycarboxylic acid (B) is
2. The bleach-fixing concentrated composition for a light-sensitive material as described in 1 above, which is a compound having a complex stability constant lower than that of the aminopolycarboxylic acid (A) with respect to a ferric salt. 3. The bleach-fixing concentrated composition for a light-sensitive material as described in 1 or 2 above, wherein the ferric aminopolycarboxylic acid complex salt is a compound represented by the following general formula [I] or general formula [II]. .

[0021]

[Chemical 3]

[In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each is a hydrogen atom, a hydroxyl group, —COOM ₃ , —PO ₃ (M ₄ ) ₂ or —CH. ₂ COO
M _5, represents a -CH ₂ OH or a lower alkyl group. However,
At least one of A ₁ , A ₂ , A ₃ and A ₄ is —COO.
_{M 3, -PO 3 (M 4} ) ₂ or -CH ₂ COOM _5. M
₁ , M ₂ , M ₃ , M ₄ and M ₅ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. n represents an integer of 0 to 2. ]

[0023]

[Chemical 4]

[In the formula, A ₁₁ , A ₁₂ , A ₁₃ and A ₄ each represent —CH ₂ OH, —PO ₃ (M ₆ ) ₂ or —COOM _7, and they may be the same or different. Good. M ₆
And M ₇ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 6, B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ]

4. 4. The bleach-fixing concentrated composition for a light-sensitive material as described in any one of 1 to 3 above, which contains a compound represented by the following general formula [III].

General formula [III] A- (COOM) _n

[In the formula, n represents 2 or 3, when n is 2, A represents a single bond or a divalent organic group, and n is 3]
In this case, A represents a trivalent organic group. M represents a hydrogen atom, an alkali metal or an ammonium group. The n M's may be the same or different. ]

5. 5. A method for processing a light-sensitive material, which comprises directly supplying the bleach-fixing concentrated composition as described in any one of 1 to 4 above to a bleach-fixing tank of a developing machine for a light-sensitive material.

6. 6. The method for processing a light-sensitive material as described in 5 above, wherein water is directly supplied to a bleach-fixing tank of a light-sensitive material developing machine.

7. In the method for processing a light-sensitive material, the bleach-fixing concentrated composition as described in any one of 1 to 4 above is directly replenished in a bleach-fixing tank or dissolved and replenished in the bleach-fixing tank.
Chloride ion concentration in bleach-fixing tank is 0.05-0.2m
A method for processing a light-sensitive material, characterized in that it is in the range of ol / L.

8. A processing method using a bleach-fixing solution obtained from the bleach-fixing concentrated composition as described in any one of 1 to 4 above, wherein a color developing step is performed before the bleach-fixing step, and a color developing composition is used in the color developing step. A method for processing a silver halide color photographic light-sensitive material, characterized in that the supply of the product to the silver halide color photographic light-sensitive material is carried out through a gas phase.

In the present specification, the bleach-fixing concentrated composition according to the present invention is used for processing a light-sensitive material by diluting it, and the processing solution used for this processing is bleach-fixed. It is called liquid.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The ferric iron complex salt of aminopolycarboxylic acid (A) used in the present invention may be any known one, but is preferably a compound represented by the above general formula [I] or [II]. is there. It is essential that the ferric iron complex salt of aminopolycarboxylic acid (A) is contained in an amount of 0.3 to 0.6 mol / L, and the ferric iron complex salt of aminopolycarboxylic acid (B) that does not form a complex salt is contained. The content mol concentration of the aminopolycarboxylic acid (B) salt is 0.01% or more and 2% or less of the content mol concentration of the ferric iron complex salt of the aminopolycarboxylic acid (A). , Achieved for the first time. Preferably, the content mol concentration of the aminopolycarboxylic acid (B) salt is 0.1% or more and 1% or more of the content mol concentration of the ferric iron complex salt of the aminopolycarboxylic acid (A).
It is the following.

The invention as set forth in claim 2 is the aminopolycarboxylic acid (A) used in the ferric iron complex salt, and the aminopolycarboxylic acid (B).
And a ferric iron complex stability constant of the aminopolycarboxylic acid (B) is lower than a complex stability constant of the aminopolycarboxylic acid (A) with respect to a ferric salt. And the object of the present invention is achieved thereby.

In addition, the ferric iron complex stability constant of the aminopolycarboxylic acid (B) is the same as that of the aminopolycarboxylic acid (A).
Is a compound lower than the complex stability constant for the ferric salt of L. G. Sillen, A .; E. Marttel
l “StabilityConstants of of
Metal-ion Complexes "TheCh
electronic Society, London (196
4), S. Chaberek, A .; E. Martell
By "Organic Sequestering Ag"
The complex stability constants of (A) and (B), which are generally known by ents ”Wiley (1959), are (A)> (B).
That is the relationship.

Preferred specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the compound represented by the general formula [I] usable in the present invention is not limited thereto. Not a thing.

[0038]

[Chemical 5]

[0039]

[Chemical 6]

The compounds represented by the above general formula [I] are disclosed in JP-A-63-267750, JP-A-63-267751, and JP-A-63-267750.
It can be synthesized by the general synthetic method described in 295954 specification.

Preferred specific examples of the compound represented by the general formula [II] used in the present invention are shown below, but the compound represented by the general formula [II] which can be used in the present invention is not limited thereto. Not a thing.

[0042]

[Chemical 7]

[0043]

[Chemical 8]

The compound represented by the general formula [II] is
Zh. Obshch. Khim. , 49, 659 (19
79), Inorganic Chemistry, V.
ol. 7, 2405 (1968), Chem. Zres
ti, 32, 37 (1978), U.S. Pat. No. 3,158,
It can be synthesized by a generally known method described in JP-A No. 635, JP-A-5-303186 and the like.

The compound represented by the general formula [II] of the present invention includes "R, R", "R, L", as optical isomers,
There are "L, R" and "L, L" bodies. These isomers can be synthesized individually or as a mixture. In the present invention, the “R, R” form is preferred.

The bleach-fixing concentrate according to the present invention may be prepared by directly replenishing the concentrate directly into the processing tank and separately replenishing with water for dilution, or in a state where the concentrate and the dilution water are mixed and diluted in the replenishment tank. You can also replenish with. The ratio of the replenishing concentrate and the diluting water in the case of directly replenishing, or the dilution rate in the case of diluting and replenishing, is the total amount of the compound represented by the general formula [I] or the general formula [II] of the present invention per liter. The content is preferably in the range of 0.05 to 2.0 mol, and more preferably in the range of 0.1 to 1.0 mol.

The above-mentioned general formula [III] used in the present invention
Specific preferred examples of the compound represented by are listed below,
The compound represented by the general formula [III] that can be used in the present invention is not limited to these.

1) HOOCCH ₂ C (OH) (COOH) CH ₂ COO
H 2) HOOC- (CHOH) ₂ -COOH 3) HOOCCH ₂ COOH 4) HOOCCH (OH) CH ₂ COOH 5) HOOCCH = CHCOOH 6) HOOCCH ₂ CH ₂ COOH 7) (COOH) ₂

[0049]

[Chemical 9]

10) NaOOCCH = CHCOONa 11) KOOCCH = CHCOOK 12) H ₄ NOOCCH = CHCOONH ₄ 13) HOOC- (1,4-cyclohexyl)-
COOH

[0051]

[Chemical 10]

16) HOOC (CH ₂ ) ₄ COOH) 17) HOOC (CH ₂ ) ₃ COOH 18) HOOC-CH (PO ₃ H ₂ ) -CH ₂ COOH 19) HOOCCH ₂ -C (COOH) (PO ₃ H ₂ )-
_{CH 2 COOH 20) HOOCCH 2 -C} (COOH) (PO 3 H 2) -
CH ₂ CH ₂ COOH

Of these, 1, 3, 4, 5, 6, 16 and 17 are preferably used in the treatment liquid of the present invention,
Especially 5 and 6. The addition amount of these compounds is preferably 1.5 mol / liter or less, more preferably 0.05 to
It is 1.0 mol / liter.

When the bleach-fixing concentrated composition of the present invention is used in an automatic processor, the bleach-fixing concentrated composition or its diluted replenisher is added to the bleach-fixing tank. The replenishing amount of the bleach-fixing solution is preferably 500 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material to be processed by adding the volumes of the replenishing water separately replenished when directly replenishing. More preferably in the range of milliliters to 400 milliliters, 40 milliliters to 35 milliliters.
The range of 0 ml is most preferable.

The chloride ion concentration in the bleach-fixing concentrated composition is designed so that the chloride ion concentration in the bleach-fixing tank in the present invention is in the range of 0.05 to 0.2 mol / L. The chloride ion may be added in the form of an alkali metal salt such as sodium chloride or potassium chloride, an ammonium salt such as ammonium chloride, or an acid such as hydrogen chloride. Chloride ion concentration is 0.07-0.15m
It is preferably in the range of ol / L, and more preferably 0.08 to 0.13 mol / L.

In designing the chloride ion concentration in such a range, the replenishing amount per 1 m ^{2 of the} silver halide photographic light-sensitive material to be processed and the elution amount from the light-sensitive material to be processed, and the bleach-fixing concentrate are designed. When adding the diluting water separately from the above, when the stabilizing solution or the overflow of the washing solution is used as the diluting water, it is set in consideration of them.

The bleach-fixing concentrated composition may contain various fixing agents, preservatives, fluorescent brightening agents, defoaming agents or surfactants other than the above.

As the fixing agent in the present invention, thiocyanate and thiosulfate are preferably used. When a thiocyanate is used as the fixing agent, the content of the thiocyanate is preferably at least 0.3 mol / l or more, and when the color negative film is treated, it is preferably 0.5 mol / l or more, particularly preferably 1.0 mol /
More than a liter. When thiosulfate is used as the fixing agent, the content of thiosulfate is preferably at least 1.0 mol / liter, and when the color negative film is treated, it is preferably 1.5 mol / liter or more.

Incidentally, silver can be recovered from the bleach-fixing solution of the present invention by a known method.

The processing time with the bleach-fixing solution of the present invention can be set arbitrarily, but is preferably 4 minutes or less.
More preferably, it is in the range of seconds to 2 minutes and 20 seconds.

In the bleach-fixing solution of the present invention, when the ratio of ammonium ion to all cations is 50 mol% or less, not only the effect of the present invention is better but also odor is reduced, so that all cations are reduced. It is one of the preferred embodiments of the present invention that the ratio of ammonium ion to 50 mol% or less. Further, the ratio of ammonium ions is preferably 30 mol% or less, and particularly preferably 10 mol% or less.

After processing the light-sensitive material with the bleach-fixing solution of the present invention, it can be washed with water or stabilized with a stabilizing solution.

The stabilizing solution preferably contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant refers to L. G. Si
llen, A .; E. "Stabil" by Martell
ity Constants of Metal-ion
Complexes "The Chemical So
citie, London (1964), S.H. Chab
erek, A .; E. "Organic" by Martell
Sequestering Agents “Wile
It means a commonly known constant such as y (1959).

The chelate stability constant for iron ions is 8
As the chelating agent as described above, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
Examples thereof include polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the above chelating agent, for example, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid , Diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid , 1,1-diphosphonoethane-2-carboxylic acid, 2-
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexametaline Examples thereof include sodium acid salt, but are not limited thereto. Of these, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like are preferable, and 1-hydroxyethylidene-1,1-diphosphonic acid is most preferable.

The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, and further 0.05
Good results are obtained in the range of up to 20 g.

Further, other compounds may be added to the stabilizing solution. Examples of these compounds include ammonium compounds. The ammonium compound may be an inorganic or organic ammonium salt, and specifically, for example, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, phosphorous acid. Ammonium, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate,
Ammonium adipate, ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate , Ammonium sulfite, ethylenediaminetetraacetate ammonium, ethylenediaminetetraacetate ferric ammonium, ammonium lactate, ammonium malate,
Ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium Etc. These may be used alone or in combination of two or more.
The amount of the ammonium compound added is preferably in the range of 0.001 to 1.0 mol, and more preferably 0.002 to 0.8 mol, per liter of the stabilizing solution.

The stabilizing solution preferably contains sulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions.
Preferred is an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. . The sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ⁻³ mol / liter, more preferably 5 × 1.
It is to be added in an amount so as to be 0 ^-3 mol / liter to 10 ^-1 mol / liter. The addition of sulfite has a preventive effect on stains in particular. The sulfite may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenisher.

In addition to the above, generally known compounds which can be added to the stabilizing solution can be added to the stabilizing solution. These compounds include polyvinylpyrrolidone (PVP)
K-15, K-30, K-90), organic acid salts (for example,
Citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, malic acid and the like), pH adjuster (for example, phosphate, borate, hydrochloric acid, sulfuric acid, etc.), antifungal agent (for example, phenol derivative, Catechol derivatives, imidazole derivatives, triazole derivatives, siabendazole derivatives, organohalogen compounds, other antifungal agents known as slime control agents in the paper-pulp industry, etc.), optical brighteners, surfactants, preservatives, Bi, Mg, Zn, Ni, Al, S
Examples thereof include metal salts such as n, Ti and Zr. One or two or more of these compounds can be arbitrarily selected and used.

A soluble iron salt may be added to the stabilizing solution. Soluble iron salt should be at least 5 × 10 in the stabilizer.
It is preferably used at a concentration of ^-3 mol / l,
It is more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / liter, and further preferably in the range of 12 × 10 ⁻³ to 1.
It is in the range of 00 × 10 ⁻³ mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenishing solution, or may be added to the stabilizing solution (tank solution) by eluting from the photosensitive material in the stabilizing solution. It may be added to the stabilizing solution (tank solution) by adhering it to the photosensitive material to be processed from the prebath and bringing it in.

The stabilizing solution may be treated with an ion exchange resin so that the calcium ion and the magnesium ion are 5 ppm or less. Further, a method of incorporating a halogen ion-releasing compound into the stabilizing solution may be used.

The pH of the stabilizing solution is preferably in the range of 5.5 to 10.0 by adding a pH adjuster. As the pH adjuster, any of generally known alkali agents or acid agents can be used.

The processing temperature for the stabilizing process is 15 ° C.
The temperature is preferably 70 ° C, more preferably 20 ° C to 55 ° C. The treatment time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds.

When stabilizing treatment is carried out by replenishing the stabilizing solution replenishing solution, the replenishing amount of the stabilizing solution replenishing solution is such that the pre-bath (bleach-fixing solution) per unit area of the light-sensitive material is taken into consideration from the viewpoint of rapid processing property and storability of dye image. 0.1 to 50 times the carry-in amount is preferable, and especially 0.
It is preferably 5 to 30 times.

The stabilizing tank for carrying out the stabilizing treatment is preferably composed of a plurality of tanks, preferably not less than 2 tanks and not more than 6 tanks, particularly preferably 2 to 3 tanks, and further preferably. It is a three-tank counter current system (a system in which the solution is supplied to the rear bath and overflows from the front bath).

When the stabilizing treatment is carried out, the rinsing treatment is not necessary, but rinsing by a small amount of rinsing in a very short time, surface washing and the like can be optionally carried out.

The light-sensitive material is subjected to color development processing prior to the processing with the bleach-fixing solution of the present invention. The color development step may be carried out by so-called tank development in which a silver halide photographic light-sensitive material to be processed is introduced into a developing tank filled with the processing solution, but it is possible to prevent deterioration of the processing solution and downsize the processing equipment. JP-A-2000-89438 and 2
A method may be used in which the amount required for the development processing exemplified by 001-166448 is supplied by means such as spraying or coating. Further, in the method of supplying the light-sensitive material by spraying or coating, the color developing replenisher can be divided into two or more parts and supplied, which is preferable from the viewpoint of storability of the replenisher.

As the color developing agent used in the color developing treatment, there are aminophenol compounds and p-phenylenediamine compounds, but it is preferable to use a p-phenylenediamine compound having a water-soluble group as the color developing agent. . These water-soluble groups in p- phenylenediamine compounds, p- has at least one phenylenediamine compound amino group or downy benzene on nuclei, as these water-soluble group, - (CH ₂₎ n- CH _{2
OH, - (CH 2) m} -NHSO 2 - (CH 2) n-C
_{H 3, - (CH 2)} m-O- (CH 2) n-CH 3, - (C
_{H 2 CH 2 O) n-} CmH 2 m +1 (m and n are each 0
Represents the above integers. ), —COOH group, —SO ₃ H group and the like are preferred. Hereinafter, specific exemplary compounds of the color developing agent will be shown.

[0079]

[Chemical 11]

[0080]

[Chemical 12]

Among the color developing agents exemplified above, preferred are (A-1), (A-2), (A-3) and (A-
4), (A-6), (A-7) and (A-15), and particularly (A-1) and (A-3).

Color developing agents are usually hydrochlorides, sulfates, p
-Used in the form of salts such as toluene sulfonate.

The amount of color developing agent added to the color developing solution is
It is preferably 0.5 × 10 ^-2 mol or more, and more preferably 1.0 × 10 ^-2 per liter of the color developing solution.
The range is 1.0 × 10 ⁻¹ mol, and most preferably 1.5.
It is in the range of × 10 ^{-2 to} 7.0 × 10 ^-2 mol.

The color developing solution may contain an alkaline agent usually used in the developing solution such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. it can. Further various additives, such as
Development modifiers such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, such as citrazinic acid, such as hydroxylamine, hydroxylamine derivatives (such as diethylhydroxylamine, disulfoethylhydroxylamine, Preservatives such as dicarboxyethylhydroxylamine), hydrazine derivatives (eg hydrazinodiacetic acid) or sulfites can be included. Furthermore, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 in tank development.
It is above, and preferably about 9 to 13.

When the solution is supplied by spraying or coating and divided into two or more liquids, p of the part containing the color developing agent is used.
H is usually 7 or less, preferably about 1 to 5. Since the color-forming property of the solution containing the color-developing agent is extremely low under acidic conditions, when all the color-developing solution parts are supplied onto the silver halide photographic light-sensitive material, the pH of the mixed solution is 7 or more, and further 9 to 9- It is preferably in the range of 13.

In the color developing solution, if necessary, as an antioxidant, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, secondary aromatic alcohol, hydroxamic acid, pentos or hexose, pyrogallol-1. , 3-dimethyl ether and the like may be combined.

Various chelating agents can be used in combination in the color developer as a sequestering agent. Examples of these chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid and ethylenediaminetetraphosphoric acid. Examples thereof include aminopolyphosphonic acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid.

The light-sensitive material to be processed with the bleach-fixing solution of the present invention has a halogenated content of 90 mol% or more, preferably 95 to 99.9 mol%, more preferably 98 to 99.9 mol% composed of silver chloride. It is preferable to have at least one silver halide emulsion layer containing silver grains. Further, the light-sensitive material is preferably one in which all layers are silver chlorobromide emulsion layers made of 98 to 99.9 mol% of silver chloride.

The crystal of the silver halide grain used in the silver halide photographic light-sensitive material may be a normal crystal, a twin crystal, or any other crystal, and has a crystal structure of [1.0.0] plane and [1.1.1] plane. Any ratio can be used. Further, 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 type) in which the inside and the outside are different. Also, these silver halides are of a type that forms a latent image mainly on the surface,
It may be of a type formed inside the particles. Further, tabular silver halide grains (JP-A-58-113934, JP-A-6-63).
No. 1-47959) can also be used.

Further, the silver halide grains may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method.

Further, for example, seed particles are prepared by an acid method, and further,
It may be a method of growing by an ammonia method having a high growth rate to a predetermined size. When growing the silver halide grains, the pH, pAg and the like in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide grains are preferably prepared as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

The silver halide emulsion layer containing silver halide grains used in the present invention contains a color coupler. These color couplers react with the color developer oxidation products to form non-diffusible dyes. The color couplers are preferably incorporated in the non-diffusive form in or in close proximity to the photosensitive layer.

Thus the red-sensitive layer may contain non-diffusible color couplers, for example cyan partial color images, generally couplers of the phenol or α-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusive color coupler that produces a magenta partial color image, usually a 5-pyrazolone-based color coupler and a pyrazolotriazole-based color coupler. The blue-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a yellow partial color image, typically a color coupler having open chain ketomethylene groups. Color couplers can be, for example, 6,4 or 2-equivalent couplers.

In the present invention, 2-equivalent couplers are particularly preferable.

Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilun).
gln ausden Forschungslabo
ratorien der Agfa), Leverkusen / Munc
-Hen), Vo1. III. p. 111 (1961)
"Color Coupler" by W. Pelz (K. Venkataraman), "The Chemistry of Synthetic Soybean" (T)
he Chemistry of Synthetic
Dyes), Vo1.4, 341-387, Academic Press, "The Theory of the Photographic Process" (The Theory of the Photo)
-Graphic Process), 4th edition, 353-
Page 362 and Research Disclosure
rch Disclosure) No. 17643, Section VII is preferred.

In the present invention, especially Japanese Patent Laid-Open No. 63-
No. 106655, p. 26, the general formula [M
-1] shown in JP-A-63-106655 as specific examples of magenta couplers.
No. of pages 29 to 34. 1-No. 77) and the general formula [C-
I] or [C-II] (specifically exemplified cyan couplers, (C'-1) to (C'-82) and (C "-1 described on pages 37 to 42)) ) ~
(C ″ -36), and high speed yellow couplers also described on page 20 (specifically exemplified yellow couplers, (Y′-1) to page 21 to 26).
(Y'-39) are preferably used in combination with the light-sensitive material of the present invention from the viewpoint of the effect of the object of the present invention.

In the present invention, when the nitrogen-containing heterocyclic mercapto compound is used in combination with the above high silver chloride light-sensitive material, not only the effect of the present invention is satisfactorily achieved but also bleaching in a color developer is carried out. The effect on the photographic performance that occurs when the fixing solution is mixed has another effect of making it extremely slight, and therefore can be mentioned as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds are described in JP-A-63-106655, Nos. 42-42.
Examples thereof include (I'-1) to (I'-87) described on page 45.

The emulsion can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred.

Reducing agents can also be used as chemical sensitizers, for example Belgian patent 493,464.
And silver compounds such as those described in U.S. Pat. No. 568,687, and polyamines such as diethylenetriamine according to Belgian Patent 547,323 or aminomethylsulfinic acid derivatives. Gold, platinum, palladium, iridium,
Noble metals and noble metal compounds such as ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is based on Zeitschrift Fair Bissenschalich Photography (Z. Wiss. Photo.) 46, 65.
72 (1951) Earl Koslovsky (R. Ko
Slovsky); and Research Disclosure No. See also 17643, Section III.

The emulsion can be spectrally sensitized by a known method. For example, cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine and the like can be used alone or in combination to perform spectral sensitization; FM Hamer's "Cyanine"・ Soybean and related compounds "(T
he Cyanine Dyes and relat
ed Compounds (1964), Ullmanns Enzyklpaded
er technischen Chemie) 4th edition,
Vol. 18, pp. 431 and following, and the above Research Disclosure No. See 17643, Section IV.

Conventional antifoggants and stabilizers can be used in the emulsion. Azaindene is a particularly suitable stabilizer, tetra and penta-azaindene being preferred,
Those substituted with a hydroxyl group or an amino group are particularly preferable. Compounds of this type are, for example, Bir.
r), Z. Wiss. Photo. (Previous) 4
7, 1952, p. 2 to 58 and the above Research Disclosure No. 17643, Section IV. The components of the light-sensitive material can be incorporated by conventional known methods; for example, US Pat. No. 2,322,0.
No. 27, No. 2,533, 514, No. 3,689, 27
No. 1, No. 3,764,336 and No. 3,765,89
See No. 7.

Components of the light-sensitive material such as couplers and UV
The absorbent can also be included in the form of a charged latex; see DE-A 2,541,274 and EP-A 14,921.

The components can also be fixed in the light-sensitive material as polymers; eg DE-A 2,043.
See 4,992, U.S. Pat. Nos. 3,370,952 and 4,080,211.

[0107]

EXAMPLES The present invention will be illustrated below with reference to examples. Example 1 A multi-layer silver halide was prepared by coating the following layers on a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the first side on the other side. A color photographic light-sensitive material was prepared. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g, 0.67 g of the additive (HQ-1) was dissolved in 6.67 g of the high boiling point organic solvent (DNP) by adding 60 ml of ethyl acetate, and the solution was added with 10 ml of 20% surfactant (SU-1) 10 % Gelatin aqueous solution 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 10 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The addition amount is expressed in g / m ² unless otherwise specified.

[0110]   7th layer (protective layer) Gelatin 1.05

[0111]   6th layer (UV absorption layer) Gelatin 0.40 Ultraviolet absorber (UV-1) 0.08 Ultraviolet absorber (UV-2) 0.04 Ultraviolet absorber (UV-3) 0.16 Anti-stain agent (HQ-1) 0.02 DNP 0.20 PVP 0.05 Irradiation prevention dye (AI-2) 0.02

[0112]   Fifth layer (red sensitive layer) Gelatin 1.15 Red-sensitive silver chlorobromide emulsion (Em-R) 0.21 Cyan coupler (C-1) 0.45 Cyan coupler (C-2) 0.25 Dye image stabilizer (ST-1) 0.20 Anti-stain agent (HQ-1) 0.01 HBS-1 0.22 DOP 0.20

[0113]   4th layer (UV absorption layer) Gelatin 0.95 Ultraviolet absorber (UV-1) 0.28 Ultraviolet absorber (UV-2) 0.11 Ultraviolet absorber (UV-3) 0.38 Anti-stain agent (HQ-1) 0.03 DNP 0.40

[0114]   Third layer (green feeling layer) Gelatin 1.45 Green-sensitive silver chlorobromide emulsion (Em-G) 0.17 Magenta coupler (MC-8) 0.35 Dye image stabilizer (ST-3) 0.15 Dye image stabilizer (ST-4) 0.12 Dye image stabilizer (ST-5) 0.18 DNP 0.20 Irradiation prevention dye (AI-1) 0.02

[0115]   Second layer (middle layer) Gelatin 1.20 Anti-stain agent (HQ-2) 0.12 DIDP 0.15

[0116]   First layer (blue sensitive layer) Gelatin 1.20 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow coupler (Y-1) 0.75 Dye image stabilizer (ST-1) 0.25 Dye image stabilizer (ST-2) 0.25 Anti-stain agent (HQ-1) 0.02 Irradiation prevention dye (AI-3) 0.01 DNP 0.20

The structural formulas of the compounds used in the above light-sensitive material are shown below.

[0118]

[Chemical 13]

[0119]

[Chemical 14]

[0120]

[Chemical 15]

[0121]

[Chemical 16]

The addition amount of the silver halide emulsion is shown in terms of silver.

(Method for preparing blue-sensitive silver halide emulsion) 4
In 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C., the following (solution A) and solution (B) were pAg = 6.5, pH = 3.
While controlling to 0, it is added simultaneously over 30 minutes.
Liquid) and (D liquid) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, the control of pAg is described in JP-A-59-45.
No. 437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

[0125]   (Liquid A) 3.45 g of sodium chloride Potassium bromide 0.04g 200 ml with water   (Liquid B) Silver nitrate 10g 200 ml with water

[0126]   (C liquid) Sodium chloride 102.8g 1.2 g of potassium bromide 600 ml with water   (D liquid) Silver nitrate 300g 600 ml with water

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation (σ / r) = 0.07, and silver chloride content. A 99.5 mol% monodisperse cubic emulsion EMP-1 was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye D-1 4.3 × 10 ⁻⁴ mol / Molar AgX sensitizing dye D-4 0.7 × 10 ^-4 mol / mol AgX

(Preparation Method of Green-Sensitive Silver Halide Emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.43 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained.

For EMP-2, the following compounds were used.
Chemical ripening was carried out at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-2 4 × 10 ⁻⁴ mol / mol AgX

(Method for preparing red-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.50 μm, coefficient of variation (σ / r) = 0.8
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-3 was obtained.

The following compounds were used for EMP-3:
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer SB-5 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye D-2 4 × 10 ⁻⁴ mol / mol AgX

[0136]

[Chemical 17]

Next, a bleach-fixing concentrated composition was prepared according to the following formulation, and EPDM (ethylene propylene rubber), EPDM: PP (polypropylene) = 9: 1 mixed rubber, which is the material of the conveying roller, and PPE (polyphenylene ether). ) Is shaped like a plate and is dipped in each liquid,
It was sealed at a porosity of 50% and stored at 40 ° C., and the degree of deterioration of the concentrated composition and the immersed material was evaluated.

The deterioration evaluation of the concentrated composition was as follows. As a result of each storage for 1 month, ◯ shows no change in liquid composition such as precipitation and precipitation. Δ is a practical range although precipitation or precipitation is slightly observed. In the case of x, precipitation or precipitation can be clearly confirmed and cannot be put to practical use.

Evaluations of EPDM, mixed rubber and PPE are as follows. As a result of each storage for 1 month, no surface alteration was observed in the circles, and the weight fluctuation of the member was 0.2% or less. Δ indicates a slight surface alteration or a weight change of less than 1.0%, which is within the practical range. × indicates that surface deterioration is clearly visible, or weight fluctuation is 1.0%
As described above, it cannot be put to practical use.

Each evaluation liquid was prepared according to the following formulation, and further filtered using a 30 μm mesh filter.
In the examples, ethylenediaminetetraacetic acid was used as EDTA,
Diethylenetetraaminepentaacetic acid is abbreviated as DTPA, and ethylenediamine disuccinic acid is abbreviated as EDDS.

[0141] Bleach-fix solution   water   Sodium sulfite 0.2 mol   Ammonium thiosulfate 1.55 mol   Compound 1 (described in Table 1) / aminopolycarboxylic acid iron complex   Compound 2 (described in Table 1) / aminopolycarboxylic acid   Succinic acid 0.03 mol   Maleic acid 0.04mol   3-mercapto-1,2,4-triazole 0.005 mol

Water was added to 1 liter, and the pH was adjusted to 6.1 with aqueous ammonia or sulfuric acid.

[0143]

[Table 1]

In the table, EDTA.Fe represents ethylenediaminetetraacetic acid ferric complex ammonium salt, and EDDS.F
e represents an ethylenediaminedisuccinic acid ferric complex ammonium salt. The results of the forced deterioration evaluation under the above conditions are shown in Tables 2 and 3.

[0145]

[Table 2]

[0146]

[Table 3]

As is clear from Tables 2 and 3, in the evaluations in which the relative ratios of compound 1 (aminopolycarboxylic acid iron complex salt) and compound 2 (aminopolycarboxylic acid) were changed, compound 2 did not depend on compound 1 In the case where the concentrated composition was not contained at all, the preservability of the concentrated composition itself was poor. Moreover, although the result that the stability of the concentrated composition is improved by containing the compound 2, as the addition amount of the compound 2 is increased,
It has been found that the influence on members constituting the processing tank, the replenishing tank, etc. increases. In addition, when a compound having a complex stability constant with iron is added to Compound 1, when a compound having a low complex stability constant is added, the concentrated composition can be stabilized, It turned out that there were few adverse effects.

Example 2 A bleach-fixing solution was prepared according to the following formulation, and the plate-shaped vinyl chloride resin and the surface material were continuously dropped onto a roller pair of EPDM having a diameter of 30 mm at a rate of 50 ml / min. Was evaluated. Each evaluation liquid was prepared according to the following formulation, and further filtered using a 30 μm mesh filter before use.

The evaluation was carried out under the conditions of a temperature of 30 ° C. and a humidity of 80% RH. The vinyl chloride resin was used in the vertical direction below the droplets at 45 °.
The angle of degree was set. Two identical rollers were used as a pair (installed facing each other), and were constantly rotated at a speed of 0.25 rpm during the evaluation.

The precipitation on the vinyl chloride board was as follows. O indicates that no precipitation occurs even after continuous dripping for 2 weeks. In the case of Δ, precipitation is observed within 2 weeks of dropping. In the case of ×, precipitation is observed within one week of dropping.

The deposition on the roller was as follows. O indicates that no precipitation occurs even after continuous dripping for 2 weeks. △ is drop 2
Precipitation is observed within a week. In the case of ×, precipitation is observed within one week of dropping.

The roller deformation was as follows. In the case of ○, no surface alteration is observed, and the weight variation of the member is 0.2% or less.
Δ indicates a slight surface alteration or a weight change of less than 1.0%, which is within the practical range. In the case of x, the surface alteration can be clearly confirmed, or the weight variation is 1.0% or more, and cannot be put to practical use. The evaluation results are shown in Table 4.

[0153] Bleach-fix solution   water   Sodium sulfite 0.2 mol   Ammonium thiosulfate 1.55 mol   Compound 1 (described in Table 4) / aminopolycarboxylic acid iron complex salt   Compound 2 (described in Table 4) / aminopolycarboxylic acid   Succinic acid 0.03 mol   Maleic acid 0.04mol   3-mercapto-1,2,4-triazole 0.005 mol

Water was added to 1 liter, and the pH was adjusted to 6.1 with aqueous ammonia or sulfuric acid.

[0155]

[Table 4]

[0156]

[Table 5]

As is clear from Table 5, the deterioration of the concentrated composition on the material when the concentrated composition is continuously supplied to each member tends to deteriorate as the concentration increases. Precipitation was severe in the concentration range of 0.7 mol or more. Further, at a low concentration of 0.2 mol or less, the deformation of the member occurred, which resulted in a problem in practical use.
From this result, a particularly good performance was obtained in the concentration range of 0.3 mol to 0.6 mol.

Further, the influence on the roller material is a practical problem because the roller surface is deteriorated due to the influence of solute in the high concentration region and fine powdery roller dust is generated. It was also found that in the low-concentration region, the rollers swell and the ends of the rollers bulge, resulting in a deformation that practically affects the carrying capacity.

Example 3 The developing device shown in FIGS. 1 and 2 (a replenishing tank for a solid replenisher is mounted on an ordinary automatic developing machine, and a tank for holding a replenishing solution is installed under a rack, In addition, a replenishing water tank is provided, and the color developing solution is prepared by adding and replenishing the replenishing solution of 3 parts (the peripheral portion of the rack and the portion related to the exposure section are omitted in FIG. 1). The same experiment as in Example 1 was performed using the above. However, the transport roller is E
Made of PDM.

Incidentally, in FIGS. 1 and 2, the photo printing machine B is used.
In the lower left part of the magazine M is set a magazine M containing photographic paper, which is an unexposed photosensitive material, in a roll. The photographic printing paper pulled out from the magazine is cut into a predetermined size through the feed roller R1 and the cutter section C to become a sheet-shaped printing paper. This sheet-shaped photographic printing paper is carried by the belt carrying means Be, and the image of the original picture O is exposed by the light source and the lens L in the exposure section E. The exposed sheet-shaped printing paper is further conveyed by a plurality of pairs of feed rollers R2, R3 and R4 and introduced into the automatic developing machine A. In the automatic developing machine A, the sheet-shaped printing paper is a color developing tank CD, a bleach-fixing tank BF, and a stabilizing tank S1 (SR-
1), S2 (SR-2), and S3 (SR-3) (substantially three-bath processing bath 1) are sequentially transported by roller transport means (reference symbol None), and color development processing and bleaching are performed, respectively. Fixing processing and stabilization processing are performed. The sheet-shaped printing paper that has been subjected to each of the above-mentioned treatments is dried in the drying unit 5'and discharged outside the machine.

Processing step: processing temperature processing time replenishment amount 1) color development processing 40 ° C. ± 0.3 ° C. 22 seconds 110 ml / m ² 2) bleach-fixing processing 38 ° C. ± 0.3 ° C. 27 seconds 40 + 100 ml / m ² 3) Stabilization treatment 38 ° C ± 0.3 ° C 27 seconds 20 + 130ml / m ² (three-tank cascade) 4) Drying 55 ° C ± 0.3 ° C 30 seconds −

The replenishing amount for the bleach-fixing treatment is the bleach-fixing replenisher 4
0 ml and 100 ml of water are added to the bleach-fix processing tank. Regarding the replenishing amount of the stabilizing treatment, 20 ml of the stabilizing replenishing agent and 130 ml of water are replenished to the stabilizing tank. The results are shown in Table 5.

Processing Solution: Color developing solution, color developing replenishing solution Processing agent for CPK-2-28 process manufactured by Konica, color developing replenishing agent 28P-1 and color developing replenishing agent starter 28.
A working solution and a replenisher were prepared using P-1S.

[0164] Bleach-fix solution   water   Sodium sulfite 0.2 mol   Ammonium thiosulfate 1.55 mol   Compound 1 (described in Table 6) / aminopolycarboxylic acid iron complex salt 0.4 mol   Compound 2 (listed in Table 6) / aminopolycarboxylic acid The addition amount is listed in Table 6   Succinic acid 0.03 mol   Maleic acid 0.04mol   3-mercapto-1,2,4-triazole 0.005 mol

Water was added to 1 liter, and the pH was adjusted to 6.1 with aqueous ammonia or sulfuric acid.

Stabilizing Solution (Tank Solution, Replenishing Solution) A new solution (tank solution) and a replenishing solution were prepared using CPK-2-28 process treating agent and stable replenishing agent 28P-3 manufactured by Konica Corporation.

The bleach-fix solution was held in a concentrated form in an automatic processor replenishing tank, and the following were used as the processing sensitizing materials, and running evaluation was carried out. Evaluation is 12 hours a day, throughput 2m
^The treatment was performed under the condition of ² / day.

(Processing Sensitive Material) The photosensitive material used in Example 1 was processed on a roll and exposed to a blackening rate of 30% before processing. The results are shown in Table 6.

The storability was evaluated as follows. As a result of continuing the continuous operation evaluation under the above conditions for one month and observing the inside of the replenishment tank, ◯ indicates no change in liquid composition such as precipitation and precipitation.
Δ is a practical range although precipitation or precipitation is slightly observed. In the case of x, precipitation or precipitation can be clearly confirmed and cannot be put to practical use.

The evaluation of sticking to the rack was as follows. As a result of continuing the continuous operation evaluation under the above conditions for one month, ◯ indicates that no precipitation or sticking occurred at the top of the rack or at the gas-liquid interface. Δ is a practical range although slight precipitation is observed at the top of the rack and at the gas-liquid interface. × is the top of the rack,
Precipitation and sticking are remarkable at the gas-liquid interface, which cannot be put to practical use.

The deterioration of the roller material was evaluated as follows. As a result of continuing the continuous operation evaluation under the above conditions for one month,
In the case of ○, no surface alteration is observed, and the weight variation of the member is 0.2% or less. Δ indicates a slight surface alteration or a weight change of less than 1.0%, which is within the practical range. In the case of x, the surface alteration can be clearly confirmed, or the weight variation is 1.0% or more, and cannot be put to practical use.

[0172]

[Table 6]

As is clear from Table 5, the result was that the storability of the bleach-fixing solution, the sticking in the processing tank due to the bleach-fixing solution, and the influence on the material were greatly improved. Also,
At the same time, as for the stabilizing process, a mechanism for separating and replenishing the replenisher and the replenishing water was provided, and as a result, the replenishment tank could be downsized and the automatic processor itself could be downsized.

Example 4 Development processing was carried out using the apparatus shown in FIG. 1 of JP-A 2000-89438.

Processing steps: Processing time Processing temperature Replenishment amount 1) Color development processing 8 seconds 60 ± 0.3 ° C. 50 ml / m ² 2) Bleach fixing processing 27 seconds 40 ° C. ± 0.3 ° C. 30 + 100 ml / m ² 3) Stable Chemical treatment 27 seconds × 3 40 ° C. ± 0.3 ° C. 20 + 130 ml / m ² (three-tank cascade) 4) Drying 30 seconds 55 ° C. ± 0.3 ° C. −

The experiment was conducted by heating the surface temperature of the photosensitive material to 60 ° C. with a heating drum having a surface temperature of 60 ° C. before supplying the color developing solution, and the replenishing amount of the bleach-fixing treatment was the bleach-fixing replenisher. 30 ml and 100 ml of water were replenished to the bleach-fixing treatment tank, and the stabilizing treatment was supplemented with 20 ml of the stabilizing replenisher and 130 ml of water.

Color development processing solution Partial solution containing color developing agent (/ liter) Water 700 ml Sodium sulfite 0.4 g Diethylenetriamine pentaacetic acid 5 sodium 0.35 g p-toluenesulfonic acid 29.5 g 4-amino-3-methyl-N- Ethyl-N- (β- (methanesulfonamide) ethyl) aniline sulfate 40.0 g Hydrolyzed to 1 liter, potassium hydroxide or sulfuric acid 5
Adjust pH to 2.0 with 0% aqueous solution.

Alkali-containing portion (/ liter) Water 600 ml Diethylenetriamine 5 acetic acid 5 sodium 2.0 g Potassium carbonate 80.0 g p-toluenesulfonic acid 18.0 g Water to 1 liter, potassium hydroxide or sulfuric acid 5
The pH is adjusted to 13.0 with 0% aqueous solution.

Bleach-fixing solution Water sodium sulfite 0.2 mol ammonium thiosulfate 1.55 mol ethylenediaminedisuccinate iron (III) ammonium 0.4 mol ethylenediamine disuccinate 0.004 mol succinic acid 0.03 mol maleic acid 0.04 mol 3-mercapto- 0.005 mol of 1,2,4-triazole was added to make 1 liter, and the pH was adjusted to 6.1 with aqueous ammonia or sulfuric acid.

Stabilizer (tank solution, replenisher) CPK-2-28 process treating agent 22P- manufactured by Konica
3 was used according to the above conditions.

As a result, in the automatic developing machine having such a structure, the processing replenishing tank can be omitted by replenishing the color developing solution through the gas phase, the downsizing of the automatic developing machine and the improvement of the storability of the processing solution can be achieved. It was found that the above can be achieved, and the effect can be further expanded by keeping the bleach-fixing solution and the stabilizing solution in a concentrated form in the automatic processor.

[Brief description of drawings]

FIG. 1 is a schematic view of an automatic processor used in Example 3.

2 is a partially enlarged explanatory view of FIG. 1, in which A shows the relationship between each processing tank and tank, and B shows the adjustment of the replenisher.

[Explanation of symbols]

A Automatic developing machine B Photographic printing machine CD Color developing tank BF Bleach-fixing tank S1, S2, S3 (SR-1, SR-2, SR-3)
Stabilization tank

Claims (8)

[Claims] 1. A silver halide photograph containing at least 0.3 to 0.6 mol / L of a ferric iron complex salt of aminopolycarboxylic acid (A) and a salt of aminopolycarboxylic acid (B) which does not form a complex salt. In the bleach-fixing concentrate for a light-sensitive material, the content mol concentration of the aminopolycarboxylic acid (B) salt is the content mol of the aminopolycarboxylic acid (A) ferric complex salt.
A bleach-fixing concentrated composition for a silver halide color photographic light-sensitive material, characterized in that the concentration is 0.01% or more and 2% or less. 2. A compound in which the aminopolycarboxylic acid used in the ferric iron complex salt of aminopolycarboxylic acid (A) and the aminopolycarboxylic acid (B) are different from each other, wherein the aminopolycarboxylic acid (B) 2. The compound having a ferric complex stability constant of 1 is lower than the complex stability constant of the aminopolycarboxylic acid (A) with respect to a ferric salt.
A bleach-fixing concentrated composition for a silver halide color photographic light-sensitive material as described in 1. 3. The ferric aminopolycarboxylic acid complex salt,
A bleach-fixing concentrated composition for a silver halide color photographic light-sensitive material according to claim 1 or 2, which is a compound represented by the following general formula [I] or general formula [II]. [Chemical 1] [In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group or —CO 2.
_{OM 3, -PO 3 (M 4} ) 2, -CH 2 COOM 5, -CH 2
Represents OH or a lower alkyl group. However, A ₁ , A ₂ , A
_At least one of ₃ and A ₄ is —COOM ₃ , —PO ₃ (M
₄ ) ₂ or -CH ₂ COOM ₅ . M ₁ , M ₂ , M ₃ , M ₄
And M ₅ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. n is 0
Represents an integer of 2. ] [Chemical 2] [Wherein A ₁₁ , A ₁₂ , A ₁₃ and A ₄ are each —CH ₂ OH,
-PO ₃ (M ₆₎ represents ₂ or -COOM _7, may each be the same or different. M ₆ and M ₇ each represent a hydrogen atom, an ammonium group, an alkali metal atom or an organic ammonium group. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n represents an integer of 1 to 6, B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. ] 4. A bleach-fixing concentrated composition for a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, which contains a compound represented by the following general formula [III]. General formula [III] A- (COOM) _n [In formula, n represents 2 or 3, when n is 2, A represents a single bond or a divalent organic group, and when n is 3, A is Represents a trivalent organic group. M represents a hydrogen atom, an alkali metal or an ammonium group. The n M's may be the same or different. ] 5. A silver halide color characterized in that the bleach-fixing concentrated composition according to any one of claims 1 to 4 is directly supplied to a bleach-fixing tank of a developing machine for silver halide color photographic light-sensitive materials. Processing method of photographic light-sensitive material. 6. The method of processing a silver halide color photographic light-sensitive material according to claim 5, wherein water is directly supplied to the bleach-fixing tank of the developing machine for silver halide color photographic light-sensitive material. 7. A method of processing a silver halide color photographic light-sensitive material, wherein the bleach-fixing concentrated composition according to any one of claims 1 to 4 is directly replenished in a bleach-fixing tank or dissolved and replenished in a bleach-fixing tank. A method for processing a silver halide color photographic light-sensitive material, wherein the chloride ion concentration in the bleach-fixing tank is in the range of 0.05 to 0.2 mol / L. 8. A processing method using a bleach-fixing solution obtained from the bleach-fixing concentrated composition according to claim 1, wherein a color developing step is carried out before the bleach-fixing step.
A method for processing a silver halide color photographic light-sensitive material, characterized in that the color developing composition is supplied to the silver halide color photographic light-sensitive material through a gas phase in the color developing step.