JPH063788A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method for a silver halide color photographic sensitive material which is stable in the pH of a bleach-fixing bath and is stable in photographic performance even if the photosensitive material is subjected to rapid processing and low replenishment processing. CONSTITUTION:The silver halide color photographic sensitive material of the method for subjecting the silver halide color photographic sensitive material to color development processing, then to bleeching and fixing processing and to washing and/or stabilizing processing has emulsion layers contg. of a high silver chloride emulsion of >=80mol% silver chloride in at least one layers and the bleach-fixing bath in the bleach-fixing processing contains aliphat. dibasic group having at least one pKa value in a 2 to 6 pKa range and having the stability constant with ferric ion smaller by 5 than the stability constant of amino-polycarboxylic acid and ferric ion. The replenishing amt. of the bleach- fixing bath is preferably specified to <=120cc per 1m<2> silver halide color photographic sensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleach-fixing method for silver halide color photographic light-sensitive materials and a processing method thereof. The present invention relates to a liquid and a treatment method thereof.

[0002]

2. Description of the Related Art Color development processing and desilvering processing are essential in processing silver halide color photographic light-sensitive materials.

Generally, in a color developing process, silver halide exposed by a color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with a coupler to give a dye image. In the desilvering process, the metallic silver produced in the color development process is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and desilvered by a fixing agent. Only the dye image remains on the light-sensitive material through the desilvering process.

In this desilvering process, a bleaching process and a stabilizing process are carried out separately, and a bleaching process and a fixing process are carried out at the same time (in the present specification, this process is referred to as a bleach-fixing process. The solution used is called a bleach-fixing solution).

In addition to the above basic steps, it usually includes various auxiliary steps such as maintaining the photographic and physical qualities of the image or improving the storability of the image. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath, each treatment step using a stabilizing bath, and the like.

In recent years, for the reason of speeding up and space saving, the desilvering process is often used as a bleaching stabilizer, and is generally widely used especially for color paper processing.

The bleach-fixing solution generally contains aminopolycarboxylic acid ferric complex salt as a bleaching agent, thiosulfate as a fixing agent and sulfite as a preservative, and acetic acid as a buffering agent. Has been done.

Acetic acid as a buffer agent is a bleach-fix solution.
It keeps pH within a certain range and stabilizes photographic performance.

That is, when a color photographic light-sensitive material (hereinafter referred to as a light-sensitive material) is color-developed and then treated with a bleach-fixing solution, the color-developing solution component which is a pre-bath component of the bleach-fixing bath is changed by the light-sensitive material. The pH of the bleach-fix solution fluctuates when brought into the bleach-fix bath. If the pH of the bleach-fix solution fluctuates, for example, if the pH becomes low, color restoration defects easily occur.
When the value becomes too high, desilvering failure, stain, etc. occur, so that it is necessary to use a buffering agent to maintain the pH within a certain range. The main functions required for the buffer agent are as described above, but in addition, it is necessary that it does not affect the photographic performance such as desilvering property and stain, and that the buffer property is always stable. .

Conventionally, acetic acid has been widely used as a buffer agent as described above, but there is a strong demand for removal of acetic acid odor due to the recent increase in environmental problems. Another problem is that acetic acid volatilizes easily, so p
H tends to fluctuate, and if a large amount of acetic acid is used to prevent it, the desilvering property deteriorates. Since such a problem becomes particularly problematic when the temperature is raised for rapid treatment or when the replenishment rate is lowered, a method of adding some compounds in place of acetic acid has been proposed.

Japanese Unexamined Patent Publication No. 4-86822 discloses a method in which an acid having a pKa of 2.0 to 6.0 is also contained in a used bleach-fixing solution in a regenerator and used as a regenerating fixing replenisher.

In this method, an aliphatic monobasic acid containing acetic acid as a pKa of 2.0 to 6.0, an amino acid monobasic acid, an aromatic monobasic acid, an aliphatic dibasic acid, an aromatic dibasic acid. Acids, etc. are disclosed. Even when the used processing solution is reused as a replenisher for the bleach-fixing solution by using the monobasic acids, acetic acid and glycolic acid, desilvering failure, color restoration failure, and cyan dye heat It is said that discoloration is less likely to occur, but as mentioned above, when acetic acid is used, pH destabilization that occurs especially when low replenishment or high temperature treatment is performed and acetic acid is desired to be environmentally free. We cannot meet the demands of users.

Further, JP-A-3-192351 discloses that a processing solution having a bleaching ability contains a polybasic acid including a dibasic acid, and
It is disclosed that by setting the ratio to H5.0 or less, it is possible to prevent magenta stain and odor after the treatment. This method is intended to improve the magenta stain generated when a ferric complex of 1,3-diaminopropanetetraacetic acid is used in a bleaching solution for a color negative film. No technical disclosure has been made regarding problems such as stability, for example, reduction in desilvering property when the replenishment rate is lowered.

As described above, one of the problems when acetic acid is used in the bleach-fixing solution is that pH cannot be stabilized. It is thought that this is because acetic acid itself volatilizes easily. Secondly, when the bleach-fixing solution is replenished at a low replenishment rate, the ratio of the color developing solution component as the pre-bath component increases, which is effective. In addition, since the increase in pH cannot be prevented, desilvering defects and stains are likely to occur, which is particularly noticeable when a photosensitive material having a high silver chloride content and having a high developing speed is used. Thirdly, as an environmental problem, it is not possible to meet the strong demand of users to control odor as much as possible.

A method using an organic acid other than acetic acid is conceivable for such a problem, but the above problems cannot be effectively solved, or molds and bacteria are found to be generated in the bleach-fixing solution or stabilizing bath. Alternatively, it has been found that some organic acids chelate-exchange with ferric aminopolycarboxylic acid complex salts and have a significant effect on photographic performance.

Therefore, an object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which can stabilize pH and photographic performance even if a useful buffering agent instead of acetic acid is used.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material in which p of the bleach-fixing solution is stable and photographic performance is stable even when rapid processing or low replenishment processing is performed. is there.

[0018]

Means for Solving the Problems In the present invention, as a result of extensive studies to achieve the above object, a silver halide color photographic light-sensitive material was color-developed and then bleach-fixed,
Then, in the method of washing with water and / or stabilizing treatment, the silver halide color photographic light-sensitive material has at least one emulsion layer comprising a high silver chloride emulsion containing 80 mol% or more of silver chloride, and the bleach-fixing method. PK for bleach-fix in processing
Contains an aliphatic dibasic acid having at least one pKa value in the range of a2 to 6 and having a stability constant with ferric ion smaller than that of aminopolycarboxylic acid and ferric ion by 5 or more. It has been found that it can be achieved by a processing method of a silver halide color photographic light-sensitive material characterized by the above. Further, in the processing method of the silver halide color photographic light-sensitive material, the replenishing amount of the bleach-fixing solution is 120 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, and the effect of the present invention is obtained. It has been found to become more prominent.

The present invention will be described in detail below.

The aliphatic dibasic acid of the present invention will be described.

At least one of the aliphatic dibasic acids used in the present invention has a pKa value in the range of pKa 2 to 6, and the stability constant of the ferric aminopolycarboxylic acid complex salt is that of the aliphatic dibasic acid ferric complex salt. It is necessary to be 5 or more higher than the stability constant.

The pKa referred to here is

[0023]

[Equation 1]

Acid dissociation constant Ka in the acid dissociation reaction
= [H ^+] [A ^-] is a logarithm of / [HA] ,, pKa = -
It is a numerical value represented by log ₁₀ Ka. Here, H ⁺ represents an acidic species, and A ⁻ is a conjugated base.

The chelate stability constant is LGSill.
en · AEMartell, “Stability Constants of Metalio
n Complexes ”, The Chemical Society, Lomdon (1964).
S. Chaberek AEMartell, “Organic Sequestering A
gents ”, Wiley (1959), etc. mean the constants generally known.

By using an aliphatic dibasic acid having a pKa value in the range of pKa 2 to 6, the exchange reaction in the film of the photosensitive material is performed more effectively than other acids, and the ferric aminopolycarboxylic acid is used. The stability constant of the complex salt is higher than the stability constant of the aliphatic dibasic acid ferric acid complex salt by 5 or more, preferably 10 or more, so that the bleaching agent, an aminopolycarboxylic acid ferric iron complex salt, and an aliphatic dibasic acid are combined. The chelate exchange reaction is controlled, and desilvering failure and color restoration failure are effectively prevented. Here, examples of combinations of the aliphatic dibasic acid and aminopolycarboxylic acid of the present invention are listed below, but the invention is not limited thereto.

Ferric ethylenediaminetetraacetic acid complex salt, diethylenetriaminepentaacetic acid ferric acid complex salt, trans-1,2-cyclohexanediaminetetraacetic acid ferric acid complex salt is oxalic acid,
Malonic acid, succinic acid, tartaric acid, malic acid, maleic acid,
There are combinations with compounds such as fumaric acid, glutaric acid, and adipic acid, β-alanine diacetate ferric iron complex salt, ethylenediaminedisuccinic acid ferric iron complex salt, nitrilotriacetic acid ferric iron complex salt, N-hydroxyethylethylenediamine triacetic acid The diiron complex salt and the glycol ether diamine tetraacetic acid ferric complex salt include combinations with oxalic acid, succinic acid, maleic acid and fumaric acid.

The amount of the aliphatic dibasic acid added is 1.5 × 10 ^{-2 to} 8.5 × 10 ^-1 mol, preferably 8.0 × 10 ^{-2 to} 4.3 × 10 ^-1 mol, per liter of the bleach-fixing solution. Is.

The ferric aminopolycarboxylic acid complex salt is used in an amount of at least 0.10 mol per liter of the bleach-fixing solution,
The content is preferably in the range of 0.3 to 0.3 mol, more preferably 0.05 to 0.25 mol / liter.

As the fixing agent used in the bleach-fixing solution according to the present invention, known fixing agents can be used, and thiocyanate and thiosulfate are preferably used.

The content of the fixing agent is preferably at least 0.1 mol / liter, more preferably 0.3 to 4 mol / liter, particularly preferably 0.5 to 3 mol / liter, and particularly preferably 0.6 to 2.0 mol / liter. It is a liter.

To the bleach-fixing solution, it is preferable to add a compound represented by the general formula [FA] or [FB] described in Japanese Patent Application No. 2-41549 and its exemplified compounds, and the effects of the present invention can be further enhanced. It is preferable not only to achieve good performance, but also to achieve ammonia-free conversion.

Further, it is preferable to add sulfite adducts represented by the general formulas [A-I] to [A-II] described in Japanese Patent Application No. 2-41549.

Incidentally, silver may be recovered from the bleach-fixing solution according to the present invention by a known method.

In addition to these fixing agents, the bleach-fixing solution may contain a sulfite salt or a pH buffering agent comprising various salts, either alone or in combination of two or more. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. In addition, compounds known to be added to ordinary bleach-fixing solutions such as alkylamines and polyethylene oxides can be appropriately added.

The bleach-fixing solution is preferably used in the range of pH 1.0 to 8.5, more preferably in the range of pH 1.5 to 8.0.

The replenishing rate of the bleach-fixing solution of the present invention is 120 ml / m ^2.
The following is preferable, and 100 ml / m ² or less is more preferable.

The color developing solution of the present invention contains a para-phenylenediamine type color developing agent. Particularly, as a color developing agent preferably used in the present invention, Japanese Patent Application No. 2-
No. 203169, pages 26 to 31 (C-1) to (C
-16), and the following compounds (C-17), (C-18),
(C-19) and the like. Among them, the color developing agent that remarkably exhibits the effects of the present invention is (C-1).

[0039]

[Chemical 1]

The color developing agent is preferably a hydrochloride salt,
Used in the form of sulfates, nitrates and p-toluenesulfonates.

The amount of the color developing agent used in the present invention is
Color developing solution per liter of 2.5 × 10 ^- 3 mol to 5.5 × 10 ^-2
It is in the range of moles, preferably 5.0 x 10 ^{-3 to} 4.5 x 10 ^-2.
There is a mole.

The color developer of the present invention has the general formula [A],
When the organic preservative represented by [B] is contained, it is preferable for rapid processing and reduction of bluing, and also the crystal protrusion on the liquid surface of the color developing solution tank is good, and another effect is exhibited. , As one of the more preferable embodiments of the present invention.

General formula [A]

[0044]

[Chemical 2]

General formula [B]

[0046]

[Chemical 3]

For a detailed explanation of the general formula [A], see Japanese Patent Application No. 2-1788.
It has the same meaning as the general formula [A] described on pages 50, 54 and 55 of the specification No. 33.

Exemplified Compounds of General Formula [A] A-1 to 15 Japanese Patent Application No. 2-178833, pages 51 to 53, page A
Same as -1 to 12 A-13 to 26 Japanese Patent Application No. 2-178833, pages 51 to 53 A
Same as −18 to 31 Next, in the general formula [B], the details of R _{1 to} R ₅ are as follows.
It has the same meaning as R _{11 to} R _{15 in} the general formula [I ′] described in Japanese Patent Application No. 2-127444, page 15, lines 1 to 16. Specific examples of the compound represented by formula [B] are shown below, but the invention is not limited thereto.

[0049]

[Chemical 4]

[0050]

[Chemical 5]

The compound represented by the general formula [A] or [B] is usually used in the form of free amine, hydrochloride, nitrate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by the general formula [A] or [B] in the color developer and the replenisher is usually 0.2 to 50 g /
1, preferably 0.5 to 30 g / l, more preferably 1 to 15
g / l.

Further, the compound represented by the general formula [A] or [B] may be used in combination with the conventionally used hydroxylamine and organic preservative, but preferably hydroxylamine is not used. It is preferable from the standpoint of developability.

The color developer of the present invention preferably contains a compound represented by the following general formula [1], [2], [3] or [4].

[0055]

[Chemical 6]

[In the formula, R ₁ represents a hydroxyalkyl group or an aminoalkyl group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a benzyl group, respectively. R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _1, or R ₁ and R ₂ and R ₃ may form a ring, respectively. ]

[0057]

[Chemical 7]

[In the formula, A and B each represent a linear or branched alkylene group, and n and m each represent an integer of 0 to 100. However, both n and m are never 0. In the general formula [1], R ₁ represents a hydroxyalkyl group which may be substituted or an aminoalkyl group which may be substituted, and the carbon number of the hydroxyalkyl group and the aminoalkyl group is preferably 1 to 10, and more preferably Is 2 to 6. As the substituent, a hydroxy group, a carboxy group, a carbonyl group, a sulfo group, a phosphono group, an ammonium group,
Examples thereof include a nitro group, an amino group and a halogen atom. R
_{Examples of 2} and R ₃ include a hydrogen atom, an alkyl group which may have a substituent, and a benzyl group which may have a substituent. A hydrogen atom, a straight chain or branched chain having 1 to 10 carbon atoms An alkyl group which may have a substituent is preferable.

As the substituent, a hydroxy group, a carboxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a ureido group, an acyl group, a cyano group, a nitro group, an amino group, a sulfo group, an alkylsulfonyl group, an alkylsulfonylamino group. , An arylsulfonyl group, an arylsulfonylamino group, a phosphono group, a phosphonate residue, and a halogen atom. Preferred are a hydroxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group and an amino group, which may be further substituted with a hydroxy group, a carboxy group, a sulfo group and an amino group.

R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₁ or R ₁ and R ₂ and R ₃ may be connected to each other to form a ring.

Preferred specific examples of the compound represented by the above general formula [1] are shown below. The present invention is not limited to these.

(1-1) Ethanolamine (1-2) Diethanolamine (1-3) Triethanolamine (1-4) Di-isopropanolamine (1-5) 2-Methylaminoethanol (1-6) 2- Ethylaminoethanol (1-7) 2-Dimethylaminoethanol (1-8) 2-Diethylaminoethanol (1-9) 1-Diethylamino-2-propanol (1-10) 3-Diethylamino-1-propanol (1-11) ) 3-Dimethylamino-1-propanol (1-12) isopropylaminoethanol (1-13) 3-amino-1-propanol (1-14) 2-amino-2-methyl-1,3-propanediol (1 -15) Ethylenediaminetetraisopropanol (1-16) benzyl ethanol (1-17) 2-amino-2- (hydroxymethyl) -1,3-propanediol (1-18) 1,3-diaminopropanol Nol (1-19) 1.3-bis (2-hydroxyethylmethylamino) -propanol

[0063]

[Chemical 8]

[0064]

[Chemical 9]

[0065]

[Chemical 10]

[0066]

[Chemical 11]

[0067]

[Chemical 12]

Among the compounds represented by the general formula [1], (1-2), (1-3),
(1-4) and (1-42).

Preferred specific examples of the compound represented by the above general formula [2] are as follows.

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

The compounds preferably used in the general formula [2] are (2-1), (2-18) and (2-26).

The amount of the compound represented by the general formula [1] or [2] added is preferably 1.0 to 100 g / l, more preferably 5.0 to 50 g / l.

[0075]

[Chemical 16]

[Wherein at least one of A to F is a sulfonic acid group or a hydroxysulfonyloxy group, or an alkali metal (sodium atom, potassium atom) salt or ammonium salt thereof, and the rest are hydrogen atoms or halogens. Represents either an atom, a saturated or unsaturated alkyl group. ]

[0077]

[Chemical 17]

[In the formula, at least one of G to N is a sulfonic acid group or a hydroxysulfonyloxy group, or an alkali metal (sodium atom, potassium atom) salt or ammonium salt thereof, and the rest are hydrogen atoms or halogens. Represents either an atom, a saturated or unsaturated alkyl group. ] The above general formula [3] or [4]
In the above, the saturated or unsaturated alkyl group representing A to F or G to N preferably has 1 to 10 carbon atoms. The carbon chain may be linear or may have a side chain.

Specific examples of the compound represented by the general formula [3] or [4] are shown below, but the invention is not limited thereto. All the exemplified compounds are shown as sodium salts,
A part or all of them may be a sulfonic acid or a hydroxysulfonyloxy form.

[0080]

[Chemical 18]

[0081]

[Chemical 19]

The addition amount of the compound represented by the general formula [3] or [4] is preferably 5 g / l or more, more preferably 10 to 200 g / l. If it is less than 5 g / l, the effect of the present invention is insufficient, and if it exceeds 200 g / l, the developability is adversely affected.

The color developer replenisher used in the present invention may contain the following developer components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate,
Potassium metaborate, trisodium phosphate, tripotassium phosphate, borax and the like can be used alone or in combination within a range where precipitation is not generated and a pH stabilizing effect is maintained. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

The color developing replenisher of the present invention preferably contains a fluorescent whitening agent. The fluorescent whitening agent not only improves the white background performance of the unexposed areas of the light-sensitive material, but also is added to the color development replenisher of the present invention to bring about good results in preventing crystal precipitation.

The fluorescent whitening agent is preferably a triazinyl stilbene type compound, and particularly preferably a compound represented by the following general formula [F].

General formula [F]

[0088]

[Chemical 20]

Detailed description of the general formula [F] is described in Japanese Patent Application No. 2-1788.
It has the same meaning as the description of the general formula [E] on pages 73 to 75 of the specification No. 33.

Exemplified Compounds of Formula [F] F-1 to 45 Japanese Patent Application No. 2-178833, pages 76 to 82 E-
Same as 1-45. The triazinyl stilbene whitening agent can be synthesized by the usual method described in, for example, "Fluorescent Whitening Agent" (published in August 1976) edited by Chemical Industry Association, page 8.

Among the exemplified compounds, F-4, F-24, F-34, F-35, F-36 and F-3 are particularly preferably used.
7, F-41.

The content of the triazinyl stilbene whitening agent is preferably 0.2 to 10 g, and more preferably 0.4 to 5 g, per liter of the color developing replenisher.

From the viewpoint of effectively achieving the object of the present invention, it is preferable to add a chelating agent represented by the following general formula [K] to the color developing replenisher of the present invention.

General formula [K]

[0095]

[Chemical 21]

For a detailed description of the general formula [K], see Japanese Patent Application No. 2-17.
It has the same meaning as the description of the general formula [K] described on pages 84 to 85 of the specification of 8833.

Exemplified compounds of general formula [K] K-1 to 22 Japanese Patent Application No. 2-178833, pages 85 to 89, K-
Same as 1-22.

In the present invention, the pH of the color developer is preferably 9.5 or more and 13.0 or less, more preferably 9.8 or more and 12.5 or less.

In the present invention, the replenishing amount of the color developing solution is 120 m.
l / m ² or less is preferable, more preferably 20 ml / m ^{2 to} 100 ml
/ M ² .

In the present invention, it is preferable to carry out the stabilizing treatment with the treating liquid having the fixing ability, without substantially washing with water following the treatment.

The stabilizing solution used in the stabilizing treatment includes the general formulas [CH-I] to [CH] described in Japanese Patent Application No. 2-41549.
-III] is preferable.

The amount of the above chelating agent used is preferably 0.01 to 100 g, and more preferably 0.05 to 5 g per liter of the stabilizing solution.
It is in the range of 0 g, particularly preferably in the range of 0.1 to 20 g.

The stabilizing solution preferably contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn,
There is a metal salt of Ti, Zr, Mg, Al or Sr, which can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate or a water-soluble chelating agent.

To the stabilizing solution, organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) are added. can do.

In the present invention, known antifungal agents can be used alone or in combination as long as the effects of the present invention are not impaired.

Further, in the treatment of the present invention, silver may be recovered from the stabilizing solution by a known method.

Further, the stabilizing solution is subjected to an ion exchange treatment, an electrodialysis treatment (see JP-A-61-28949) and a reverse osmosis treatment (JP-A-60).
-240153 and JP-A-62-254151).
Further, it is also preferable to use water used for the stabilizing solution which has been previously deionized. That is, the mildew resistance of the stabilizing solution, the stability of the stabilizing solution, and the image storability are improved. Any means can be used for the deionization treatment as long as it makes Ca, Mg ions less than 5 ppm in the wash water after treatment. For example, the treatment with an ion exchange resin or a reverse osmosis membrane can be used alone or in combination. preferable. Regarding the ion exchange resin and the reverse osmosis membrane, Open Technical Report 87-1984 and Open Technical Report 89-2051
It is described in detail in No. 1.

No washing treatment is required after the stabilizing treatment, but rinsing, surface washing and the like can be optionally performed by washing with a small amount of water within an extremely short time.

In the present invention, the pH of the stabilizing solution is 5.5 to 10.
A range of 0 is preferred. PH that can be contained in the stabilizing solution
The preparation agent can be any of the commonly known alkaline agents or acid agents.

The treatment temperature during the stabilization treatment is 15 ° C to 70 ° C.
C is preferable, and more preferably in the range of 20 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.

The replenishing amount of the stabilizing solution is preferably from 0.1 to 80 times the carry-in amount of the pre-bath (fixing solution or bleach-fixing solution) per unit area of the light-sensitive material, from the viewpoints of rapid processing property and storability of dye image.
0.5 to 30 times is preferable.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, and particularly preferably 2 to 3 tanks in a counter current system (supplied to the post-bath. It is preferable to adopt a method of overflowing from the previous bath).

Next, a color light-sensitive material to which the present invention is applied will be described.

As the silver halide grains in the light-sensitive material, silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol% or more,
Particularly preferably, those containing 95 mol% or more, and most preferably those containing 98 mol% or more are used.

The silver halide emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 10 mol% or less. , Is more preferably 5 mol% or less, still more preferably 2 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol% or less, most preferably zero. is there. Silver chloride 90 like this
The silver halide grains mainly composed of silver chloride containing more than 1 mol% may be applied to at least one silver halide emulsion layer, but is preferably applied to all the photosensitive silver halide emulsion layers. .

The crystals of the silver halide grains may be normal crystals, twin crystals or other crystals, and have a [1.0.0] plane and a [1.
Any ratio can be used for the [1.1] plane. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, layers (phases) with different inside and outside
It may be in the shape of a core (core / shell type).
Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-11393)
No. 4, Japanese Patent Application No. 59-170070) can also be used.
Further, silver halides described in JP-A 64-26837, 64-26838, 64-77047 and the like can be used.

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

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method with a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and an amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521, for example. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention contains a color coupler.

The red-sensitive layer can contain, for example, non-diffusible color couplers which produce cyan partial color images, generally phenol or α-naphthol based couplers. Green sensitivities can include, for example, at least one non-diffusible color coupler that produces a magenta partial color image, usually a 5-pyrazolone-based color coupler and pyrazolotriazole. The blue-sensitive layer is, for example, at least one non-diffusible color coupler that produces a yellow partial color image,
Color couplers having open chain ketomethylene groups can generally be included. The color coupler can be, for example, a 6,4 or 2 equivalent coupler.

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

Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilunglnan For.
schungslaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.111
(1961) W.Pelz's "Farbkuppler"; K. Venkataraman, "The Chemitsry of Syntlietic"
Dyes), Vol.4, 341-387, Academic Press (Aca
demic Press), "The Theory of the Photogra"
Phic Process), 4th edition, pages 353-362; and Research Disclosure No. 17643, Section VII.

In the present invention, in particular, JP-A-63-106 is used.
No. 655, page 26.
1]] (Specific examples of these magenta couplers are disclosed in JP-A-63-106655, 2
No. 1 to No. 77 described on pages 9 to 34 are mentioned. ), The general formula [CI] or [CI] also described on page 34.
Cyan coupler represented by the formula (I) (Specific examples of the cyan coupler include (C'-
1) to (C'-82) and (C "-1) to (C" -36)), and high-speed yellow couplers also described on page 20 (specifically exemplified yellow couplers). (Y-1) to (Y'-39) described on pages 21 to 26) are preferably used from the viewpoint of the effect of the object of the present invention.

When a nitrogen-containing phosphine ring-containing mercapto compound is used in a light-sensitive material using an emulsion mainly composed of silver chloride, not only the effect of the present invention is satisfactorily achieved but also a bleach-fix solution is contained in a color developing solution. The effect on photographic performance that occurs when mixed,
Since it has another effect of making it extremely slight, it can be mentioned as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing phosphine-containing mercapto compounds include (I'-1) to (I'-87) described on pages 42 to 45 of JP-A-63-106655.

The silver halide emulsions may be prepared by conventional methods (eg single or double inflow with constant or accelerated rush of material). Especially preferred is the double influx method of adjusting pAg; see Research Disclosure No. 17643, Sections I and II.

The silver halide 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 patents 493,464 and 5
Silver compounds as described in 68,687, and eg Belgian patents
Polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives according to 547,323. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is the Zeitschrift Fair
Bissen Schalich Photography (Z.Wiss.Pho
to.) 46 , 65-72 (1951) R. Kosiovsky's paper; and Research Disclosure No. 17643, Section III above.
See also

The emulsion mainly composed of silver chloride is an optically known method,
It can be sensitized with conventional polymethine dyes such as neutraocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like; FM Hamer, " Cyanine Dyes and rel
ated Compounds) (1964) Ullmanns Hemy
Enzyklpadie der technischen Chimie) 4th edition, 18 volumes, 4
See page 31 and beyond, and Research Disclosure No. 17643, section IV above.

For the emulsion mainly containing silver chloride, conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer, tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this type are described, for example, in Birr's paper, Zeitschrift-Für-Bissen-Schagliche Photography (Z.Wiss.Photo).
47, 1952, p.2-58, and Research Disclosure No. 17643, supra, Section IV.

The components of the light-sensitive material can be incorporated by a conventional method known in the art; for example, US Pat. No. 2,322,027.
Nos. 2,533,514, 3,689,271, 3,764,366 and 3,765,897. It may also be included in the components of the light-sensitive material, for example in the form of couplers and UV absorbers or charged latexes; see DE-A 2,541,274 and EP-A 14,921. The components can also be fixed in the light-sensitive material as polymers; for example DE 2,044,922, US Pat. Nos. 3,370,952 and 4,
See 080, 211.

The support of the color photographic light-sensitive material used in the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, such as a glass plate, Examples thereof include polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films and the like, and other usual transparent supports may be used.

These supports were appropriately selected according to the purpose of use of the light-sensitive material, but in order to more effectively achieve the object of the present invention, a reflective type support such as baryta paper, polyethylene-coated paper, or polypropylene composite is used. It is preferable to use the body.

The present invention can be applied to color films such as color papers, color negative films, color reversal films, color reversal papers, direct positive color papers, color films for movies, color films for televisions, etc. which are used for general use or movies. It can be applied to photosensitive materials.

The processing method of the present invention is effective for any automatic developing machine, but the opening area (surface area of the liquid per liter of the processing liquid) is 12 cm ² / l or less, preferably 10 c.
The effect of the present invention becomes remarkable when it is m ² / l or less.

[0135]

The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited thereto.

Example 1 Each layer of the following constitution was coated on a paper support by laminating polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side. A silver halide color photographic light-sensitive material (1) 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, additive (H
Q-1) 0.67 g, anti-aging dye (AI-
3) is added to 6.5 g of high boiling organic solvent (DNP) and 60 m of ethyl acetate.
l was added and dissolved, and this solution was mixed with 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 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,
A layer coating solution was prepared.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0140]

[Table 1]

[0141]

[Table 2]

[0142]

[Chemical formula 22]

[0143]

[Chemical formula 23]

[0144]

[Chemical formula 24]

[0145]

[Chemical 25]

[0146]

[Chemical formula 26]

[0147]

[Chemical 27]

[Method for preparing blue-sensitive silver halide emulsion] 40
In 1000 ml of 2% gelatin aqueous solution kept at ℃, the following (A
30) while controlling the liquids) and (B liquid) to pAg = 6.5 and pH = 3.0
Simultaneously added over a period of time, and further add the following (C liquid) and (D liquid)
Simultaneous addition was performed over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

At this time, a control solution having the following composition was used for controlling pAg. The composition of the control solution is a mixed silver halide salt aqueous solution consisting of sodium chloride and potassium bromide, the ratio of chloride ion and bromide ion is 99.8: 0.2, and the concentration of the control solution is mixture of solution A and solution B. 0.1 mol / l when mixing, and 1 mol / l when mixing liquid C and liquid D.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10.0 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added 600 ml (solution D) 300 g of silver nitrate Water was added and after 600 ml was added, desalting was performed using 5% aqueous solution of Demol Na and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with gelatin aqueous solution. Average particle size 0.85μm,
A monodisperse cubic emulsion EMP-1 having a coefficient of variation (σ / r) of 0.07 and a silver chloride content of 99.5 mol% 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 STAB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX BS− 2 1 × 10 ⁻⁴ mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
m, a coefficient of variation (σ / r) = 0.08, and a monodisperse cubic emulsion EMP-2 having a silver chloride content of 99.5 mol%.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° 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 STAB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX [red Preparation Method of Sensitive Silver Halide Emulsion] (Liquid A) and (B
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
m, a coefficient of variation (σ / r) = 0.08, and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5 mol%.

For EMP-3, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-5 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 4 × 10 ⁻⁴ mol / mol AgX The silver chloride content of the color paper sample prepared as described above was 99.5 mol%.

This silver chloride content was changed as shown in Table 3 to prepare and use an experimental color paper sample.

This sample was subjected to wedge exposure according to a conventional method,
A running process was performed according to the following process step (1).

Processing process (1) Temperature (° C) Processing time Replenishment amount (ml / m ² ) (1) Color development 38.5 45 seconds 80 (2) Bleach fixing 35 to 37 45 seconds 54 (3) Stable * 30 to 37 30 seconds x 3 180 (4) Drying 60-80 30 seconds- [Color development tank solution and replenisher] Color development tank solution Replenisher Additive (2-18) 10g 15g Aromatic sulfonic acid (3-2) 20g 30g potassium bromide 3.0 × 10 ^-4 mol 1.5 × 10 ^-4 mol of potassium chloride 4.0 × 10 ^-2 mol - potassium sulfite 5.0 × 10 ^-4 mol 1.0 × 10 ^-3 mol color developing agent (C-1) 1.5 × 10 - ² mol 1.0 × 10 ^-3 mol Diethylhydroxylamine 3.5g 5.0g Potassium carbonate 30g 30g Diethylenetriaminepentaacetic acid 1.0g 1.0g Phosphor brightener (F-34 below) 1.5g 1.5g pH 10.10 10.60

[0161]

[Chemical 28]

[Bleach-fixing tank and replenisher] color developing tank replenisher replenisher ethylenediaminetetraacetic acid ferric ammonium salt 0.15 mol 0.30 mol ethylenediaminetetraacetic acid 2.0 g 2.0 g ammonium thiosulfate 75 g 150 g ammonium sulfite 45 g 90 g additive (see Table 3) ) 0.13 mol pH 5.50 5.30 [stabilizing tank solution and stabilizing replenisher] stabilizing tank solution and replenisher o-phenylphenol 0.15g ZnSO ₄ · 7H ₂ O 0.2g ammonium sulfite (40%) 5.0 ml 1-hydroxyethylidene-1,1 -Diphosphonic acid (60% solution) 3.8g Ethylenediaminetetraacetic acid 2.0g Optical brightening agent (Tinopearl SFP Ciba Geigy) 2.0g pH 7.80g Running processing is performed using NPS-1411 small automatic developing machine as an automatic developing machine. The processing solution was filled, and the replenishment solution was continuously processed while being replenished with a metering pump.

The running processing amount was 0.1 round per day until the total replenishment amount of the stabilizing solution was 3 times the developing tank solution. One round means that the bleach-fixing replenisher for the capacity of the bleach-fixing tank is replenished.

At the end of running, the unexposed color paper sample and the exposure-exposed color paper sample were processed, and after the processing, the reflection density at 1000 nm was measured using an infrared densitometer, and the desilvering property was evaluated as follows. It was performed by the formula.

Desilvering property = Reflection density of exposed sample−Reflection density of unexposed sample Further, the difference in fluctuation in pH of the bleach-fix solution at the start and end of running was evaluated.

Further, the halftone-exposed photosensitive material was processed at the end of running, and the degree of occurrence of processing unevenness at the tip portion thereof was evaluated according to the following evaluation criteria.

○ Not generated △ Slightly generated × Very generated Results are shown in Table 3.

[0168]

[Table 3]

As is clear from the results shown in Table 3, the bleach-fix solution was not formed even after the low replenishment treatment was performed for the first time in the combination of the present invention.
It is possible to establish a processing method in which the fluctuation of pH is small, uneven processing does not occur, and desilvering is excellent.

Example 2 The same experiment as in Example 1 was carried out except that the processing step was changed to (2) below and the running processing was carried out using an automatic processor NPS-808SQA (Konica Corp.).

The results are shown in Table 4. Processing process (2) Temperature (° C) Processing time Replenishment amount (ml / m ² ) (1) Color development 38.0 25 seconds 116 (2) Bleach fixing 35-37 25 seconds 200 (3 ) Stable * 30 to 37 25 seconds x 3 200 (4) Drying 60 to 80 30 seconds- * There are 3 stabilizing tanks, and the counter current system is used.

[0172]

[Table 4]

As is clear from the results in Table 4, even in the ultra-rapid processing, the combination of the present invention established an excellent processing method for desilvering and occurrence of processing unevenness.

Example 3 Similar to Experiment No. 7 of Example 1, except that the combination of the ethylenediaminetetraacetic acid ferric ammonium salt and the additive 1 in the bleach-fix solution was changed to equimolar amounts as shown in Table 5. When the experiment was conducted, almost the same results were obtained except that the pH fluctuation of the treatment solution was slightly increased.

[0175]

[Table 5]

Example 4 The same experiment as in Experiment No. 7 of Example 1 was conducted except that the addition amount of the additive 1 was changed as shown in Table 6. The results are shown in Table 6.

[0177]

[Table 6]

As is clear from Table 6, the addition amount of the aliphatic dibasic acid is preferably 1.5 × 10 ^{-2 to} 8.5 × 10 ^-1 mol / l, more preferably 8.0 × 10 ^{-2 to} 4.3 × 10 ^-1. Mol / l.

Example 5 The same experiment as in Experiment No. 7 of Example 1 was conducted, except that the aromatic sulfonic acid was changed to the compound shown in Table 6 and the running treatment speed was reduced to 0.05 rounds per day. The results are shown in Table 7.

[0180]

[Table 7]

As is clear from Table 7, in the processing method of the present invention, it can be confirmed that the effect of the present invention is further enhanced by adding an aromatic sulfonic acid or an aromatic sulfonic acid ester to the color developing solution.

Example 6 An experiment was carried out under the same conditions except that the replenishing amount of the bleach-fix solution of Example 1 was set to the conditions shown in Table 8 below and the running speed was 0.03 R per day. The results are shown in Table 9.

[0183]

[Table 8]

[0184]

[Table 9]

As is apparent from Table 9, the effect of the present invention is more remarkable as the replenishing amount of the bleach-fixing solution is smaller, and 120 ml / m ² or less is preferable.

[0186]

According to the present invention, there is provided a method for processing a silver halide color photographic light-sensitive material in which the pH of the bleach-fixing solution is stable and the photographic performance is stable even after rapid processing or low replenishment processing. You can

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material is color-developed and then bleach-fixed, and then washed with water and / or
Alternatively, in the stabilizing method, at least one layer of the silver halide color photographic light-sensitive material contains 80 mol% of silver chloride.
It has an emulsion layer consisting of the above high-silver chloride emulsion, and has at least one pKa value in the range of pKa 2 to 6 in the bleach-fixing solution in the bleach-fixing treatment, and has a stability constant with ferric ion of amino. A method for processing a silver halide color photographic light-sensitive material, which comprises an aliphatic dibasic acid having a stability constant of 5 or more smaller than that of a polycarboxylic acid and ferric ion. 2. The processing method according to claim 1, wherein the replenishing amount of the bleach-fixing solution is 120 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material in the processing method of the silver halide color photographic light-sensitive material. .