JPH05119453A - Treating method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deposition of solid matter or deposition of foreign matter by incorporating a compd. expressed by specified formula into a stabilizer liquid and specifying the amt. of replenisher for the stabilizer liquid to a specified value or below. CONSTITUTION:A silver halide color photographic sensitive material is treated with a liquid having fixing performance and then treated with a stabilizer liquid. This stabilizer liquid contains a compd. selected from compds. expressed by formula I. Further, the amt. of replenisher for the stabilizer liquid is specified to <=670ml/m<3>. In formula I, Z represents atoms required to form a carbon ring or heteroring, X is a aldehyde group or a group expressed by formula II, and n is an integer 1-4. In formula II, R1 and R<2> are lower alkyl groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material which does not cause precipitation while suppressing fading of dyes and enables stable processing. It relates to a method of processing a material.

[0002]

2. Description of the Related Art Generally, a silver halide color photographic light-sensitive material is subjected to image development, color development processing, bleaching, fixing or bleach-fixing processing, which has fixing ability, and then stabilization, washing, etc. Is processed by. In the water washing step following the treatment with the processing solution having the fixing ability, thiosulfate which is a compound which reacts with silver halide to form a water-soluble complex salt, other water-soluble silver complex salt, and further as a preservative It is known that the sulphite, metabisulphite, etc. are contained in, adhered to, and brought into the light-sensitive material, and when the amount of washing water is small, the image storability is adversely affected.

Therefore, in order to eliminate such drawbacks,
In reality, a large amount of running water is used to wash away the salt from the light-sensitive material. However, in recent years, for economic reasons such as shortage of water resources, soaring sewerage charges and utility costs, and pollution reasons, there is a demand for a treatment process in which the amount of washing water is reduced and pollution measures are taken.

Conventionally, as a countermeasure against these problems, for example, a method in which a water washing tank has a multi-stage structure and water flows countercurrently is described in West German Patent 2,92.
0,222 and S.R.Gold Basser (SRGol
dwasser), "Water Flow Rate in Immersion-Washing of
Motion-picture Film) ”SMPTE. Vol.64, pp. 248-253, Ma
y. (1955) etc.

Further, a preliminary washing with water is provided immediately after the fixing bath,
There is also known a processing method for reducing the amount of pollutant contained in and attached to the light-sensitive material and entering the washing step, and reducing the amount of washing water. However, these techniques are not treatment methods that do not use flush water at all.

Accordingly, in recent years, water resources are exhausted, and the cost for washing with water is increasing due to price increases of crude oil and the like, which is becoming a serious problem.

On the other hand, there is also known a processing method in which a stabilization process is carried out immediately after photographic processing without washing with water. For example, a silver stabilizing treatment with a thiocyanate described in US Pat. No. 3,335,004 is known. However, this method has a drawback that a large amount of inorganic salt is contained in the stabilizing bath, so that the surface of the light-sensitive material is stained after drying.

It has also been found that when these stabilizing treatments are carried out, there is another drawback that the dye image is deteriorated during long-term storage.

On the other hand, when processing a color photographic light-sensitive material for photography represented by a photographic light-sensitive material in which the silver halide is silver iodobromide, a stabilizing bath containing formaldehyde is generally used in the final processing step following the washing bath. Has been.

The formaldehyde used in the stabilizing bath prevents physical properties of the color photographic light-sensitive material, especially scratches on the surface of the color photographic light-sensitive material and changes in gradation due to the photographic light-sensitive material being gradually hardened over time. It is known that there is an effect of improving the stability of the dye image due to the unreacted coupler remaining in the color photographic light-sensitive material.

However, formaldehyde, which is added to the stabilizing bath for the purpose of stabilizing the dye image, adheres to the light-sensitive material and forms an adduct with sulfite ion brought in from the previous bath (processing solution having fixing ability). However, not only the effect of stabilizing the dye image, which is the original purpose, is reduced, but there is also a drawback that the sulfurization is promoted. In order to solve these problems, U.S. Pat.
It has been proposed to use an alkanolamine as shown in Japanese Patent No. 3, but the use of the alkanolamine tends to adversely affect the yellow stain in the unexposed area, and it cannot be said that the sulfuration preventing effect is sufficient. There wasn't.

Regarding formaldehyde, in the United States, CIIT (Chemical Industry Association Toxicology Research Institute) has announced that nasal cavity cancer occurred in rats at 15 ppm formaldehyde, and NIOSH (National Institute of Occupational Safety and Health). , ACGIH (Meeting of Government Specialists in Industrial Hygiene) said that cancer may occur.

Formaldehyde is also strongly regulated in Europe, and in West Germany it has been regulated to reduce formaldehyde to 0.1 ppm or less in homes for 10 years.

Further, in Japan, formaldehyde has a harmful effect on mucous membranes due to stimulant action on deleterious substances, drugs, and organic solvent poisoning regulation of labor safety law or regulation on household products, regulation on fiber and plywood. Since 1975, the Ministry of Health and
Formaldehyde regulation has come to be enforced, and a technique capable of reducing formaldehyde has been long awaited.

Further, in recent years, Process C-41 developed by Eastman Kodak Company for the purpose of speeding up treatment and saving bath.
Processes for color negative films called B and C-41RA are known. This process consists of (color development process)-(bleaching process)-(fixing process)-(stabilizing process)-(drying process), and is a rapid process which is substantially not washed with water.

As a stabilizer for formaldehyde in the stabilizing solution (stabilizer) used in this stabilizing step, for example, as described in JP-A-63-244036, 62-27742 and 61-151538, hexa The use of methylenetetramine compounds and hexahydrotriazine compounds is known.

On the other hand, in the industry, the frequency of dissolution of the processing liquid by the laboratory worker is reduced (especially in large-scale laboratories), the storage place of the processing liquid is reduced,
It is highly desired to reduce the amount of replenisher due to the reduction of pollution load due to the reduction of waste liquid and the demand for improvement of working environment.

However, when the amount of the replenisher for the stabilizing solution is reduced, the residence time of the stabilizing solution in the stabilizing tank of the automatic developing machine becomes long, and the thiosulfate is easily decomposed due to air oxidation or the like, and fine sulfurization occurs. Problems such as black precipitation of substances, flocculent floating substances, adhered substances on the wall of a tank, and generation of tar have been highlighted.

Further, when this treatment liquid is used, there is a problem that after the completion of drying, tar often sticks to the film, and scratches and foreign matters are attached to cause a serious problem that cannot be recovered.

A technique for solving such a problem is proposed in JP-A-2-153348 and the like. This technology
After treatment with a processing solution having a fixing ability with thiosulfate 1.1 to 2.0 mol / l as a fixing agent, it contains at least one of hexamethylenetetramine and its derivative, hexahydrotriazine and its derivative, and N-methylol compound. When treated with a stabilizing solution, the processing stains are eliminated.

However, this technique merely suggests a possibility, and when it is actually applied to a low replenishment processing of a light-sensitive material, it can sufficiently solve the problems of black precipitation due to sulfide and flocculent floating matter. I knew I couldn't.

[0022]

Therefore, the object of the present invention is not only to provide stable processing characteristics even when the replenishing amount to the stabilizing solution is low, but also to make conventional formaldehyde unnecessary. Preventing the precipitation of sulfides in the stabilizing solution, the generation of flocs and tars, and the adhesion of adherents to the wall of the stabilizing tank while suppressing the fading of the dye, and the adhesion of tars and scratches to the photosensitive material. Another object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which can prevent the adhesion of foreign matter.

Other objects will be apparent in the following specification.

[0024]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of intensive studies to achieve the above object. That is, the method for processing a silver halide color photographic light-sensitive material according to the present invention is a method for processing a silver halide color photographic light-sensitive material, which comprises treating a silver halide color photographic light-sensitive material with a processing solution having fixing ability and then processing it with a stabilizing solution. In the method, the stabilizing solution contains a compound selected from the compounds represented by the following general formula [F], and the replenishing amount of the stabilizing solution is 670 ml / m ² or less.

General formula [F]

[0026]

[Chemical 3]

In the formula, Z represents an atomic group necessary for forming a carbocycle or a heterocycle, X represents an aldehyde group,

[0028]

[Chemical 4]

(R ₁ and R ₂ each represent a lower alkyl group), and n represents an integer of 1 to 4.

As a result of various investigations by the present inventors, the use of the compound represented by the general formula [F] in the stabilizing solution makes it possible to stabilize the dye image without using conventionally used formalin. I understood. In addition, when a low-replenishment running process with a stabilizing solution containing formalin is continuously carried out for a long period of time, black sulfide precipitates in the stabilizing solution, cotton-like suspended matter, generation of tar, tank However, there is a problem in that the wall surface of the sheet is stuck. However, by using the compound represented by the general formula [F] in the stabilizing solution,
Further, it was found that the above problems do not occur when a low replenishment running of the stabilizing solution at a replenishment rate of 670 ml / m ² or less is performed for a long time.

The present inventors believe that the more difficult the automatic developing machine becomes, the more difficult the maintenance becomes and the more serious the problem becomes. Therefore, in order to solve such various problems, the above-mentioned JP-A-2-153348 has been proposed. A study was made on the technology described in the publication, but it was found that a complete solution could not be found within the scope of such technology.

The above problems are not limited to the stabilizing solution,
It has been found that the object of the present invention can be achieved more effectively by changing the composition of the processing liquid itself having fixing ability. That is, in the technique described in JP-A-2-153348, only thiosulfate is used as a fixing agent, but by using thiosulfate and thiocyanate in combination, the object of the present invention can be achieved more effectively. It is also clear that this is one of the preferred embodiments of the present invention.

Next, the compound represented by the general formula [F] used in the present invention will be explained. In the general formula [F], Z represents an atom group necessary for forming a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocycle, and the carbocycle and the heterocycle are monocyclic or condensed rings. And Z is preferably an aromatic carbocycle or heterocycle having a substituent. The substituent of Z is an aldehyde group, a hydroxyl group, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), an aralkyl group, an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.). , Halogen atom, nitro group, sulfo group, carboxy group, amino group (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), hydroxyalkyl group, aryl group (eg, phenyl, p- Methoxyphenyl, etc.), cyano group,
Aryloxy groups (eg, phenoxy, p-carboxyphenyl, etc.), acyloxy groups, acylamino groups, sulfonamide groups, sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.), carbamoyl groups (Eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.) or a sulfonyl group (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.) is preferable.

The carbocycle represented by Z is preferably a benzene ring, and the heterocycle represented by Z is preferably 5.
Is a 6-membered or 6-membered heterocycle, for example, a 5-membered ring is thiophene, pyrrole, furan, thiazole, imidazole, pyrazole, succinimide, triazole, tetrazole, etc., and a 6-membered ring is pyridine,
Pyrimidine, triazine, thiadiazine, etc. are respectively mentioned.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole and quinoline.

Preferred examples of the compound represented by formula [F] are shown below.

[0037]

[Chemical 5]

The exemplified compounds (F-1) to (F-52) can be obtained by inserting various substituents into 1 to 6 in the above formula as shown in the following table.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Chemical 6]

[0043]

[Chemical 7]

Other specific examples of compounds include the compound examples (76) described on pages 13 to 14 of Japanese Patent Application No. 3-89686.
~ (90).

Among the specific examples of the compounds represented by the general formula [F], more preferable compounds are (F-2),
(F-3), (F-4), (F-6), (F-23), (F-24),
(F-52) and (F-61) are mentioned, but most preferably
(F-3) can be mentioned.

The compound represented by the general formula [F] can be easily obtained as a commercial product.

The compound represented by the general formula [F] is contained in the stabilizing solution for silver halide color photographic light-sensitive materials. The treatment liquid used in the pre-bath of the treatment bath having a bleaching ability together with the stabilizing solution within a range that does not impair the effects of the present invention,
It may be contained in a processing solution having a bleaching ability, a processing solution having a fixing ability, and the like.

The amount of the compound represented by the general formula [F] added is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g per liter of the stabilizing solution.

The compound represented by the general formula [F] is characterized in that it has good image storability even under conditions of low humidity, as compared with known formaldehyde substitute compounds.

The replenishing amount of the stabilizing solution is 6 per 1 m ² of the light-sensitive material.
It is 70 ml or less, preferably 100 ml or more and 500 ml or less, and more preferably 160 ml to 460 ml. If the stabilizing solution replenishment amount exceeds 670 ml, the amount of waste liquid increases,
It is not preferable in terms of social environment and economy, and the effect of the present invention is not remarkable, and the effect of the present invention becomes more remarkable as the replenishment becomes lower with a limit of 100 ml / m ² .

In the present invention, the replenishment amount means a substantial replenishment amount, and when regenerating, the replenishment amount of the regenerant becomes the replenishment amount.

In the present invention, the stabilizing solution has a pH of 6.0 or higher, preferably 7.0 or higher, more preferably 7.5 to 9.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of generally known alkali agents or acid agents.

In the present invention, 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 is
LGSillen and AEMartell, “Stability Constants
of Metal-ion Complexes ”, The Chemical Sociery, Lo
ndon (1964), S. Chaberek. AEMartell, "OrganicSeq
uestering Agents ", Willey (1959), etc. mean a constant generally known.

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 include, but are not limited to, the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,
5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate and the like, and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and the like. Yes, among them 1
-Hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 1 liter of the stabilizing solution.
A preferable result is obtained in the range of 0.01 to 50 g, and more preferably in the range of 0.05 to 20 g.

As a preferable compound added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds,
Specifically, it is ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium phosphate or the like. These may be used alone or in combination of two or more.
Addition amount of ammonium compound is 0.001 per liter of stabilizing solution.
The range is preferably 1.0 to 1.0 mol, more preferably 0.002 to 2.
It is in the range of 0 mol.

Further, the stabilizing solution preferably contains sulfite. The sulfite may be any organic or inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite,
Mention may be made of potassium metabisulfite, ammonium metabisulfite and hydrosulfite.

The sulfite is at least 1 × in the stabilizing solution.
It is preferable to add such an amount that it becomes 10 ^-3 mol / l, more preferably 5 × 10 ^-3 to 10 ^-1 mol / l, especially for stain. There is a preventive effect. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

The stabilizing solution preferably contains a metal salt in combination with the chelating agent. Such metal salts include B
a, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, T
There are metal salts of i, 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. The amount used is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably 4 × 10 ⁻⁴ to 2 × 10 ⁻² mol per liter of the stabilizing solution.

Stabilizers include organic acid salts (citrate, acetate, succinate, oxalate, benzoate, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.). ) Etc. can be added. The amount of these compounds added depends on the pH of the stabilizing bath.
Any combination may be used in an amount within the range necessary to maintain the stability and not adversely affecting the stability during storage of color photographic images and the occurrence of precipitation.

In the present invention, a known fungicide such as 5-chloro-2-methylisothiazolin-3-one or benzisothiazoline may be used in combination with the stabilizer of the present invention within a range not impairing the effects of the present invention. You can

The stabilizing solution preferably contains a surfactant. As the surfactant, the compound represented by the general formula [II] described on page 6 of Japanese Patent Application No. 2-274026 is preferable, and specific examples thereof include the water-soluble organic siloxane compounds shown below. preferable. In addition, JP-A-62
The compounds represented by the general formulas [I] to [II] described in JP-A-250449 may be used.

[0064]

[Chemical 8]

[0065]

[Chemical 9]

Other specific exemplified compounds include (II-2) described on pages 67 to 70 of Japanese Patent Application No. 2-274026.
(II-4) to (II-6), (II-8) to (II-12), (II
-14).

The amount of the water-soluble organic siloxane compound having a polyoxyalkylene group added exhibits a good effect when used in the range of 0.01 to 20 g per liter of the stabilizing solution.

If it is less than 0.01, stains on the surface of the light-sensitive material are conspicuous, and if it exceeds 20 g, a large amount of the organosiloxane compound adheres to the surface of the light-sensitive material, resulting in acceleration of stains.

In the process of the present invention, silver may be recovered from the stabilizing solution. In addition, 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).
-241053, 62-254151, JP-A-2-132440)
It is also a preferable mode to carry out the present invention that the treatment is carried out by the above method. Further, it is also preferable to use deionized water used in the stabilizing solution in advance. 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 or equal to 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 It is preferable to use them together. Ion exchange resins and reverse osmosis membranes are described in detail in Technical Report No. 87-1984.

The salt concentration in the stabilizing solution is preferably 1000 ppm or less, more preferably 800 ppm or less in order to achieve the effects of the present invention.

The presence of a soluble iron salt in the stabilizing solution is preferable for achieving the effects of the present invention.

Soluble iron salt should be present in the stabilizing solution at least 5 × 10 ⁻³
It is preferably used in a concentration of mol / l, more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / l, further preferably 12 × 10 ^{−3 to} 100 × 10 ⁻³ mol / l. The range is l.

The treatment temperature for the stabilization treatment is 15 to 70 ° C.
Is preferable, and more preferably in the range of 20 to 55 ° C. The treatment time is preferably 150 seconds or less, more preferably 3 to 120 seconds, and most preferably 6 to 90 seconds.

The stabilizing tank 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 2 tanks. It is preferable to use a system in which the solution is supplied to the post-bath and overflows from the pre-bath.

In the present invention, even if the opening area of the stabilizing tank is widened, there is an effect that sulfidation hardly occurs. That is,
It was thought that when the opening area of the stabilizing tank was widened, sulfurization was likely to occur, but according to the treatment of the present invention, even if the opening area was widened, sulfidation was difficult to occur.

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

The preferred processing steps in the processing method using the processing liquid of the present invention are: color development → bleach-fixing → stable color development → bleach → fixing → stable color development → bleach → bleach-fixing → stable color development → bleach-fixing → Fixing → Stable Color development → bleach fixing → bleach fixing → stable Color development → bleach → bleach fixing → fixing → stable are preferable, and the steps of and are particularly preferable. That is, in the present invention, the processing solution having a fixing ability includes the bleach-fixing solution, the bleaching-fixing solution, the bleaching solution and the bleaching-fixing solution, the bleaching-fixing solution and the fixing solution, and the bleaching-fixing solution depending on the processing steps as described above. Examples of the processing solution include bleach-fixing solution and a combination thereof, and the processing solution having fixing ability is preferably a fixing solution in the present invention.

The bleaching agent preferably used in the bleaching solution or the bleach-fixing solution in the present invention is a ferric iron complex salt of an organic acid represented by the following general formula [A].

[0080]

[Chemical 10]

The compound represented by the general formula [A] will be described in detail below.

A _{1 to} A ₄ may be the same or different and each represents --CH ₂ OH, --COOM or --PO ₃ M ₁ M ₂ , and M and M.
₁ and M ₂ each represent a hydrogen atom, an alkali metal atom (for example, sodium atom, potassium atom) or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.). Examples of the substituent of the alkylene group include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.

Preferred specific examples of the compound represented by the above general formula [A] are shown below.

[0084]

[Chemical 11]

Other specific examples of the compound include (A-2) described on pages 89 to 90 of Japanese Patent Application No. 2-274026,
(A-3), (A-5) to (A-8), (A-10) to (A
-12).

As the ferric iron complex salts of the compounds (A-1) to (A-12), sodium salts, potassium salts or ammonium salts of these ferric iron complex salts can be optionally used. From the viewpoint of the effect and solubility of the object of the present invention,
Ammonium salts of these ferric complex salts are preferably used.

Of the above compound examples, the compound (A-1) is particularly preferably used in the present invention.

In another preferred embodiment of the present invention, the bleaching agent has a sufficiently high oxidizing power, and bleach fog is likely to occur in the case of an ammonium salt. Can be used in an amount of 20 mol% or less, particularly preferably 10 mol% or less.

The amount of the ferric organic acid complex salt added is preferably in the range of 0.1 to 2.0 mol, and more preferably in the range of 0.15 to 1.5 mol / l, per liter of the bleaching solution.

The second organic acid represented by the general formula [A]
When using iron complex salts and other organic acid ferric iron complex salts such as ethylenediaminetetraacetic acid in combination of two or more,
From the viewpoint that the effect of the present invention is better exhibited, it is preferable that the ferric complex salt of the compound represented by the general formula [A] accounts for 70% or more, more preferably 80% or more, and particularly preferably It is preferably 90% or more, and most preferably 95% or more.

The organic acid iron (III) complex salt may be used in the form of a complex salt, or an iron (III) salt such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, Phosphoric acid second
An iron (III) ion complex salt may be formed in a solution using iron or the like and aminopolycarboxylic acid or a salt thereof. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. Further second
When a complex salt is formed in a solution using an iron salt and aminopolycarboxylic acid, one type or two or more types of ferric iron may be used. Furthermore, one or more aminopolycarboxylic acids may be used.

In any case, the aminopolycarboxylic acid may be used in excess to form the iron (III) ion complex salt.

For the bleaching solution or the bleach-fixing solution, Japanese Patent Application No. 63-489
The effect on rapidity by containing at least one of the compounds represented by imidazole and its derivative or the general formulas [I] to [IX] described in No. 31 and these exemplary compounds Can play.

In addition to the above bleaching accelerator, Japanese Patent Application No. 60-263568
Exemplified compounds described on pages 51 to 115 of the specification and JP-A Nos. 63-17445 and 63-95630, 53-95630 The compounds described in JP-A-28426 can be similarly used.

These bleaching accelerators may be used alone or in combination of two or more, and the addition amount is generally preferably in the range of 0.01 to 100 g per liter of the bleaching solution, and more preferably.
It is 0.05 to 50 g, and particularly preferably 0.05 to 15 g.

When a bleaching accelerator is added, it may be added and dissolved as it is, but it is generally dissolved in water, an alkali, an organic acid or the like in advance and then added. If necessary, methanol or ethanol is added. It can also be added by dissolving it in an organic solvent such as acetone.

The temperature of the bleaching solution or the bleach-fixing solution is preferably 20 to 50 ° C, preferably 25 to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less.

The pH of the bleaching solution is the pH of the processing bath during processing of the silver halide photographic light-sensitive material, and is the so-called replenishing solution pH.
It can be clearly distinguished from H.

Halides such as ammonium bromide, potassium bromide and sodium bromide are usually added to the bleaching solution or the bleach-fixing solution before use. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained.

The replenishing amount of the bleaching solution is preferably 500 ml or less, preferably 20 ml to 400 ml, and most preferably 40 ml to 3 per 1 m _{2 of the} silver halide color photographic light-sensitive material.
It is 50 ml, and the effect of the present invention becomes more remarkable as the replenishment amount becomes lower.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air may be blown thereinto or oxygen may be blown thereinto, if desired, in the processing bath and the processing replenisher storage tank, or suitable oxidation may be carried out. Agents such as hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

Further, a member having high oxygen permeability, such as silicone rubber, can be used as a pipe of an automatic processor.

Next, it is preferable that the fixing solution or the bleach-fixing solution in the fixing step adopted after the bleaching step contains at least thiocyanate as a fixing agent, and it is a combination of thiosulfate and thiocyanate. Good. The thiocyanate is preferably 0.3 mol / l or more,
3.0 mol / l is more preferable.

The replenishing amount of the fixing solution or the bleach-fixing solution according to the present invention is preferably 900 ml or less per 1 m ² of the light-sensitive material, more preferably ^{20 to} 750 ml, and particularly preferably 50 to 620 ml per 1 m ² of the light-sensitive material.

P of the fixing solution or the bleaching solution fixing solution according to the present invention
H is preferably in the range of 4-8.

A fixing solution or a bleach-fixing solution is disclosed in Japanese Patent Application No. 63-48931.
The compound represented by the general formula [FA] described on page 56 of the specification and its exemplified compounds may be added.
The compounds represented by formula (1) or (2) described on pages 5 to 10 of WO91 / 08517 may be used, and a small amount of a light-sensitive material is processed for a long period of time using a bleach-fixing solution or a fixing solution. Another effect is that sludge generated during the process is extremely small.

A favorable effect is obtained when the amount of the compound represented by the general formula [FA] and the compound represented by the general formula (1) or (2) added is within the range of 0.1 to 200 g per liter of the treatment liquid.

Sulfites and sulfite-releasing compounds may be used in the fixer or the bleach-fixer. Specific examples of these compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite. Further, Japanese Patent Application No. 63-48931 specification 60
The compounds represented by the general formula [B-1] or [B-2] on the page are also included.

These sulfites and sulfite-releasing compounds are used as sulfite ions of at least 0.05 per liter of the fixer.
The amount is required to be mol, but a range of 0.08 to 0.65 mol / l is preferable, and a range of 0.10 to 0.50 mol / l is particularly preferable. A range of 0.12 to 0.40 mol / l is particularly preferable.

The processing time with the processing solution having fixing ability according to the present invention is optional, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 3 minutes and 15 seconds, and particularly preferably 20 seconds. ~ 3 minutes range.

In the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the stabilizing solution, the processing solution having fixing ability and the bleaching solution. The reason is that not only the effects of the object of the present invention are better exhibited, but also rapid processing suitability is obtained. Here, the forced liquid agitation means that agitation means is added and the liquid is forcibly agitated, instead of the normal diffusion movement of the liquid. As a forced stirring means, Japanese Patent Laid-Open No.
The means described in JP-A-222259 and JP-A 1-206343 can be adopted.

In the present invention, the crossover time between each tank such as the fixing tank to the stabilizing tank is within 10 seconds, preferably within 7 seconds, which is an effect different from the present invention. Further, a method of installing a duck hill valve or the like to reduce the processing liquid brought in by the light-sensitive material is also a preferable embodiment for carrying out the present invention.

A silver halide color photographic light-sensitive material (hereinafter referred to as "light-sensitive material" if necessary) to which the processing method of the present invention is applied.
Alternatively, the silver halide grains used as the "sensitizer" may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, and silver iodobromide is effective in achieving the effect of the present invention. Is preferably used.

The average silver iodide content of all silver halide emulsions in the light-sensitive material is preferably 0.1 to 15 mol%, more preferably 0.5 to 12 mol%, and particularly preferably 1 to 10 mol%.
Is.

The average grain size of all silver halide emulsions in the light-sensitive material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm.
m.

The silver halide emulsion is (grain size / grain thickness)
In the case where grains having an average value of less than 5 are included, the grain size distribution is preferably monodisperse in view of desilvering property.

The monodisperse silver halide emulsion is an emulsion in which the weight of silver halide contained in the grain size range of ± 20% around the average grain size is 60% or more of the total weight of silver halide grains. , Preferably 70% or more, more preferably 80% or more.

Here, the average particle size is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri becomes the maximum (the effective digit is 3 digits, the minimum digit is Round off 4).

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

The particle size can be obtained, for example, by enlarging the particles from 10,000 to 50,000 times with an electron microscope, and measuring the particle diameter or the area at the time of projection on the print (measurement). The number of particles is indiscriminately 1000 or more).

A particularly preferred highly monodisperse emulsion is one having a distribution width defined by (standard deviation / average grain size) × 100 = distribution width (%) of 20% or less,
It is more preferably 15% or less.

The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane 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 (see JP-A-58-113934 and JP-A-59-170070) can also be used.

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

Alternatively, for example, a method of forming seed particles by an acidic method and further growing by an ammonia method having a high growth rate to grow them to a predetermined size may be used. When growing the silver halide grains, the pH, pAg, etc. 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, for example, JP-A-54-48521. It is preferable to successively inject and mix the halide ion with the halide ion.

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.

Furthermore, in the silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion is a
What is described in Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following shows the locations of description.

[Item] [Page of RD308119] Iodine composition 993 I-A manufacturing method 993 I-A and 994 E crystal habit Normal crystal 993 I-A twin Twin 〃 Epitaxial 〃 Halogen composition uniform 993 I- Item B Non-uniform 〃 Halogen conversion 994 IC item 〃 Substitution 〃 Metal content 994 I-D item Monodisperse 995 IF item Solvent addition 〃 Latent image forming position Surface 995 I-G item 〃 Applicable negative material 995 Item IH Positive (including internal fog grains) 〃 Mixed emulsion 995 IJ Item Desalting 995 II-A In the present invention, the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization. Use what you have done. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

The following are the places of description.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 Item III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographs that can be used in the present invention Additives are also described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C 25-26 Light absorber 1003 VIII 25-26 Light-scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Various light-sensitive materials used in the present invention Couplers can be used, specific examples of which are described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D item VII C-G magenta coupler 1001 VII-D item VII C-G item Cyan coupler 1001 VII-D item VII C To G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F alkali soluble coupler 1001 VII-E The additive used in the present invention is It can be added by the dispersion method described in XIV of RD308119.

In the present invention, the above-mentioned RD17643 page 28, RD
The supports described in 18716 pages 647-8 and RD308119, X IX can be used.

The light-sensitive material may be provided with auxiliary layers such as the filter layer and the intermediate layer described in the item VII-K of RD308119. The photosensitive material is RD308119 VII-K.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section can be adopted.

In the present invention, the effects of the present invention are more effectively exhibited when a vinyl sulfone type hardener is used in the light-sensitive material.

The vinyl sulfone type hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, and preferably a vinyl group bonded to a sulfonyl group or a vinyl group capable of forming a vinyl group. It has at least two groups.

For example, the compound represented by the following general formula [VS-I] is preferably used in the present invention.

General formula [VS-I] L- (SO ₂ X) m In the above general formula [VS-I], L represents an m-valent linking group, and X represents —CH═CH ₂ or —CH ₂ CH. ₂ represents Y, Y
Represents a group capable of leaving in the form of HY by a base, such as a halogen atom, a sulfonyloxy group, a sulfooxy group (including a salt), a residue of a tertiary amine, and the like. m represents an integer of 2 to 10, and when m is 2 or more, —SO ₂ —X may be the same or different from each other.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (for example, alkylene, alkylidene, alkylidyne or the like, or a group formed by combining these), an aromatic hydrocarbon group (for example, arylene or the like, or A group formed by combining these), -0-, -NR'- (R 'represents a hydrogen atom or preferably an alkyl group having 1 to 15 carbon atoms), -S-,> N-,- CO-, -SO-, -SO ₂ -or -SO
_3- is a m-valent group formed by combining one or more of the bonds shown by-, and when two or more -NR'- are included, their R's combine to form a ring. May be.

The linking group L further includes those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

As a specific example of X, --CH = CH ₂ or --CH
₂ CH ₂ Cl and the like are preferable.

Typical examples of vinyl sulfone type hardeners are shown below.

[0143]

[Chemical 12]

Specific examples of compounds other than these include:
See pages 122 to 128 of Japanese Patent Application No. 2-274026 (VS
-1), (VS-3), (VS-5), (VS-7), (V
S-8), (VS-11), (VS-13), (VS-21),
(VS-23) to (VS-32), (VS-34) to (VS-5
3) and (VS-55) to (VS-57).

The vinyl sulfone type hardener used in the present invention is, for example, German Patent 1,100,942 and US Patent 3,490,9.
Aromatic compounds such as those listed in No. 11, etc.
No. 44-29622, No. 47-25373, No. 47-24259, etc., alkyl compounds bonded with a hetero atom, as described in
Sulfonamides, ester compounds as described in JP-B-47-8736, 1,3,5-tris [β- (vinylsulfonyl) as described in JP-A-49-24435, etc.
Propionyl] -hexahydro-s-triazine or alkyl compounds such as those described in JP-B-50-35807, JP-A-51-44164 and the like, and compounds described in JP-A-59-18944, etc. Include.

These vinyl sulfone type hardeners are dissolved in water or an organic solvent and used in an amount of 0.005 to 20% by weight, preferably 0.02 to 10% by weight, based on the binder (eg gelatin). A batch method or an in-line addition method is adopted for addition to the photographic layer.

The layer in which these hardeners are added to the photographic layer is not particularly limited, and may be added to, for example, one uppermost layer, one lowermost layer or all layers.

Further, in the present invention, the silver halide color photographic light-sensitive material preferably contains at least one of the compounds represented by the following general formulas [B-1] to [B-3].

[0149]

[Chemical 13]

In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amino group, a carboxylic acid group (including a salt thereof) or a sulfonic acid group (including a salt thereof). R ² and R ³ are each a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including salts thereof).
Alternatively, it represents a sulfonic acid group (including a salt thereof). M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0151]

[Chemical 14]

[0152]

[Chemical 15]

In the formula, R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, or -R ¹²
-OR ¹³ , -CONHR ¹⁴ (wherein R ¹² represents an alkylene group, R ¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group or an arylalkyl group) or an arylalkyl group, and R ⁵ and R ⁶ Each represents a hydrogen atom, a halogen atom, a halogenated alkyl group or an alkyl group, and R ⁷
Is a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Halogenated alkyl group, an arylalkyl group, -R ¹⁵ -O
Represents R ¹⁶ or —CONHR ¹⁷ (wherein R ¹⁵ is an alkylene group,
The hydrogen atom of both R ¹⁶ and R ¹⁷ represents an alkyl group. ), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amino group or a nitro group.

Specific examples of the compound represented by the general formula [B-1] include the following exemplified compounds.

[0155]

[Chemical 16]

Other specific examples include Japanese Patent Application No. 2740/1990.
(B-1-4) to (B-
1-15) and (B-1-17).

Some of the compounds represented by the above general formula [B-1] are known as antiseptics such as mandarin orange and are commercially available, and those skilled in the art can easily obtain them.

Of the above-exemplified compounds, preferred compounds are
(B-1-1), (B-1-2), (B-1-3), (B-1
-4) and (B-1-5).

The general formula [B-1] used in the present invention.
The compound is preferably used in an amount of 0.03 to 50 g, more preferably 0.12 to 10 g, and particularly preferably 0.15 to 5 g per liter of the stabilizing solution of the present invention.

Specific examples of the compound represented by the above general formula [B-2] or [B-3] will be described below.
It is not limited to these.

(B-2-1) 2-Methyl-4-isothiazolin-3-one (B-2-2) 5-chloro-2-methyl-4-isothiazolin
-3-one (B-2-3) 2-methyl-5-phenyl-4-isothiazolin-3-one (B-2-4) 4-bromo-5-chloro-2-methyl-4-isothiazolin-3 -One (B-2-5) 2-hydroxymethyl-4-isothiazolin-3-one (B-2-6) 2- (2-ethoxyethyl) -4-isothiazolin-3-one (B-2-7 ) 2- (N-Methyl-carbamoyl) -4-isothiazolin-3-one (B-2-8) 5-bromomethyl-2- (N-dichlorophenyl-carbamoyl) -4-isothiazolin-3-one (B-2 -9) 5-chloro-2- (2-phenylethyl) -4-isothiazolin-3-one (B-2-10) 4-methyl-2- (3,4-dichlorophenyl)-
4-isothiazolin-3-one (B-3-1) 1,2-benzisothiazolin-3-one (B-3-2) 2- (2-bromoethyl) -1,2-benzisothiazolin-3-one ( B-3-3) 2-Methyl-1,2-benzisothiazoline-
3-one (B-3-4) 2-ethyl-5-nitro-1,2-benzisothiazolin-3-one (B-3-5) 2-benzyl-1,2-benzisothiazolin-3-one ( B-3-6) 5-Chloro-1,2-benzisothiazoline-
3-one These exemplified compounds are U.S. Pat.No. 2,767,172, U.S. Pat.No. 2,767,173, U.S. Pat.No. 2,767,174, U.S. Pat.No. 2,870,015, U.K. Pat. , Etc., synthesis methods and examples of application to other fields. There are also some that are on the market, and Topside 300 (Permachem Asia
Topside 600 (Permachem Asia Co., Ltd.),
Fine Side J-700 (Tokyo Fine Chemical Co., Ltd.), P
It is available under the trade name of roxel GXL (ICI Corporation).

The compounds represented by the general formulas [B-1] to [B-3] are used in the range of 0.1 to 500 mg, preferably 0.5 to 100 mg, per 1 m ² of the light-sensitive material.

Further, these compounds represented by [B-1] to [B-3] may be used in combination of two or more kinds.

The present invention is a color photographic light-sensitive material such as a color paper, a color negative film, a color reversal film, a color reversal paper, a direct positive color paper, a movie color film and a television color film which are used for general use or for movies. Can be applied to.

[0165]

EXAMPLES Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

Example 1 A multilayer color photographic light-sensitive material sample was prepared by sequentially forming each layer having the following composition from the support side on a triacetyl cellulose film support.

The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. However, the sensitizing dye is shown by the number of moles relative to 1 mole of silver halide in the same layer.

(Photosensitive Material Sample) First Layer; Antihalation Layer Black Colloidal Silver 0.2 UV Absorber (UV-1) 0.23 High Boiling Solvent (Oil-1) 0.18 Gelatin 1.4 Second Layer; First Intermediate Layer Gelatin 1.3 3 layers; low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) 1.0 Sensitizing dye (SD-1) 1.8 × 10 ⁻⁵ (mol / silver 1 mol) Sensitizing dye (SD-2) 2.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-3) 3.0 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.70 Colored cyan coupler (CC -1) 0.066 DIR compound (D-1) 0.03 DIR compound (D-3) 0.01 High boiling solvent (Oil-1) 0.64 Gelatin 1.2 4th layer; Medium-sensitive red-sensitive emulsion layer Silver iodobromide emulsion (average grain size) 0.7 μm, AgI 8.0 mol%) 0.8 Sensitizing dye (SD-1) 2.1 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (SD-2) 1.9 × 10 ^-4 (mol / silver 1 mol) Sensation (SD─3) 1.9 × 10 ^-4 (mol / mole of silver) Cyan Coupler (C─2) 0.28 Colored cyan coupler (CC─1) 0.027 DIR compound (D─1) 0.01 High-boiling solvent (Oil─1) 0.26 Gelatin 0.6 Fifth layer; High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.8 μm, AgI 8.0 mol%) 1.70 Sensitizing dye (SD-1) 1.9 × 10 ^-5 (mol / silver 1 mol) ) Sensitizing dye (SD-2) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-3) 1.7 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.05 Cyan Coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.02 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.17 Gelatin 1.2 6th layer; 2nd intermediate layer Gelatin 0.8 7th layer; Low Sensitive green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) 1.1 Sensitizing dye (SD-4) 6.8 × 10 ^-5 (mol / silver 1 mol) Sensitizing dye (SD- ⁵ ) ) 6.2 × 10 ^-4 (Mo / Silver 1 mol) Magenta coupler (M-1) 0.54 Magenta coupler (M-2) 0.19 Colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling solvent ( Oil-2) 0.81 Gelatin 1.8 Eighth layer; Medium-speed green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.7 μm, AgI 8.0 mol%) 0.7 Sensitizing dye (SD-6) 1.9 × 10 ^-4 (mol Sensitizing dye (SD-7) 1.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-8) 1.5 × 10 ^-5 (mol / silver 1 mol) Magenta coupler (M-- 1) 0.07 Magenta coupler (M-2) 0.03 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling solvent (Oil-2) 0.30 Gelatin 0.8 9th layer; High sensitivity green-sensitive emulsion layer Iodine silver bromide emulsion (average grain size 1.0 .mu.m, AgI 8.0 mol%) 1.7 sensitizing dye (SD─6) 1.2 × 10 ^-4 (mol / mole of silver) sensitizing dye (SD─7) 1.0 ^10-4 (mol / mole of silver) Sensitizing dye (SD─8) 3.4 × 10 ^-6 (mol / mole of silver) Magenta Coupler (M─1) 0.09 Magenta Coupler (M─3) 0.04 Colored magenta coupler ( CM-1) 0.04 High boiling point solvent (Oil-2) 0.31 Gelatin 1.2 10th layer; Yellow filter layer Yellow colloidal silver 0.05 Color contamination inhibitor (SC-1) 0.1 High boiling point solvent (Oil-2) 0.13 Gelatin 0.7 Formalin scavenger (HS-1) 0.09 Formalin scavenger (HS-2) 0.07 11th layer; low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.4 μm, AgI 2.0 mol%) 0.5 Silver iodobromide emulsion (average grain Diameter 0.7 μm, AgI 8.0 mol%) 0.5 Sensitizing dye (SD-9) 5.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-10) 1.9 × 10 ^-5 (mol / silver 1 mol) Yellow coupler (Y-1) 0.65 Yellow coupler (Y-2) 0.24 DIR compound (D-1) 0.03 High boiling solvent (Oil ─ 2) 0.18 Gelatin 1.3 Formalin scavenger (HS-1) 0.08 12th layer; High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.0 μm, AgI 8.0 mol%) 1.0 Sensitizing dye (SD-9) 1.8 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-10) 7.9 × 10 ^-5 (mol / silver 1 mol) Yellow coupler (Y-1) 0.15 Yellow coupler (Y-2) 0.05 High boiling point Solvent (Oil-2) 0.074 Gelatin 1.30 Formalin scavenger (HS-1) 0.05 Formalin scavenger (HS-2) 0.12 13th layer; 1st protective layer Fine grain silver iodobromide emulsion (average grain size 0.08 μm, AgI 1.0 mol%) ) 0.4 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.13 Formalin scavenger (HS-2) 0.37 Gelatin 1.3 14th layer; 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Sliding agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, Mw: 100000 and Mw:
1100000 of two kinds of AF-2 were added.

The emulsion used in the above sample was a monodisperse surface low silver iodide-containing emulsion, and was optimally subjected to gold / sulfur sensitization according to a conventional method. The average particle size is shown as a particle size converted into a cube.

[0170]

[Chemical 17]

[0171]

[Chemical 18]

[0172]

[Chemical 19]

[0173]

[Chemical 20]

[0174]

[Chemical 21]

[0175]

[Chemical formula 22]

[0176]

[Chemical formula 23]

[0177]

[Chemical formula 24]

After subjecting the film sample thus produced to actual exposure using a camera, the stabilizing solution replenishment amount was changed as shown in Tables 4 and 5, and a running test was conducted under the following conditions.

Treatment process Treatment time Treatment temperature Complementary amount Color development 3 minutes 15 seconds 38 ° C 775ml Bleach 45 seconds 38 ° C 155ml Settling 1 minute 30 seconds 38 ° C 500ml Stabilization 50 seconds 38 ° C As shown in Table 4 and Table 5 Drying 1 min 40-70 ° C- (Replenishment amount is the value per 1 m ² of light-sensitive material.) However, the stabilization process uses a 2-tank countercurrent method, and the final tank of the stabilizing solution is replenished It was carried out by a method in which the overflow flows into the previous tank. Furthermore, a part (275 ml / m ² ) of the overflow of the stabilizing tank following the fixing tank was poured into the fixing tank.

The composition of the processing liquid used in the above processing step is as follows.

Color developing solution Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl- N- (β-hydroxylethyl) aniline sulfate 4.6 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 10.01 with potassium hydroxide or 20% sulfuric acid.

Color development replenishing solution Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate Salt 6.0 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2 g Add water to make 1 liter, and adjust to pH 10.20 with potassium hydroxide or 20% sulfuric acid.

Bleaching tank liquid 1,3-Propylenediaminetetraacetic acid Ferric ammonium (Ex. A-1 ferric ammonium complex salt) 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Glacial acetic acid 40 g Ammonium nitrate 40 g Water was added. To 1 liter using ammonia water or glacial acetic acid
Adjust to pH 4.4.

Bleach Replenisher 1,3-Propylenediaminetetraacetic acid ferric ammonium salt (Exemplary A-1 ferric ammonium complex salt) 0.32 mol Ethylenediaminetetraacetic acid disodium 2 g Ammonium bromide 120 g Ammonium nitrate 50 g Glacial acetic acid 40 g Water was added. To 1 liter using ammonia water or glacial acetic acid
Adjust to pH 3.4.

Fixing tank solution and fixing replenishing solution Ammonium thiocyanate 120 g

[0186]

[Chemical 25]

Ammonium thiosulfate 100 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4 g Ethylenediaminetetraacetic acid disodium 1 g Water was added to make 1 liter, pH was adjusted using glacial acetic acid and aqueous ammonia.
Adjust to 6.5.

Stable tank solution and stable replenisher solution Surfactant 0.5 g

[0189]

[Chemical formula 26]

Deerside 702 (manufactured by Deaphone) 1.0 ml Additive (I) Described in Table 4 and Table 5 Water was added to make 1 liter, and pH was adjusted to 7.5 with potassium hydroxide and 20% sulfuric acid. ..

The running treatment was carried out until the amount of the stable replenisher solution that was twice the capacity of the stable tank tank was replenished (0.07 per day).
R (R = total amount of replenisher / tank volume)) A small running experiment developing machine was used. At the end of the running process, the state of precipitation of sulfide in the stable tank, the state of tar generation and the state of adhered substances on the wall surface of the tank, and the stains, scratches and foreign substances on the processed film sample after the running process were confirmed. I observed. In addition, the magenta density of the highest density portion of the processed film sample was measured, and then stored at 70 ° C. and 70% relative humidity for 10 days, and the maximum magenta density after storage was measured to obtain the fading rate of the dye. The results are summarized in Tables 4 and 5.

The evaluation criteria were set as follows. (Even after Example 2) [Evaluation Criteria] Presence or absence of precipitation of sulfide ○ None at all △ No precipitation on the liquid surface, but it may be confirmed as floating matter and may be a problem in practical use × Floating matter, precipitation × × Floating matter and precipitate, and the number of [x] fixed on the liquid interface of the rack increases, indicating that the amount of precipitation is large.

Generation of tar ○ None at all △ There is a slight problem in practical use × Many Yes Presence or absence of sticking ○ No at all △ There is no problem as a product × Cannot be commercialized × × Completely commercialized No Stain after processing ○ No at all △ There is no problem as a product × Cannot be made into a product × No scratches or foreign matter adhered after processing ○ No at all △ There is a slight problem as a product × Cannot be made as a product × × No product at all Can't

[0194]

[Table 4]

[0195]

[Table 5]

From Tables 4 to 5 above, using the compound of the present invention (compound represented by the general formula [F]),
It can be seen that the desired effects of the present invention are satisfactorily achieved at 670 ml / m ² or less.

Further, when the replenishing amount of the stabilizing solution is more than 670 ml / m ² , the effect is not good enough and the amount of the waste solution increases, which is not preferable in the social environment, and the increasing amount of the stabilizing solution causes It is not preferable in terms of cost.

Example 2 Using the sample prepared in Example 1, the following compound (water-soluble organic siloxane compound) was added to the stabilizing solution of Experiment No. 1-19.

[0199]

[Chemical 27]

A running experiment was performed in the same manner as in Example 1 except for the above.

As a result, the fading rate of magenta was the same, but the precipitation of sulfide, the flocculent suspension, the stain after the treatment, the scratches, and the adhesion of foreign matter were all "O", and the present invention was further improved. ..

The above-exemplified compounds (1) and (3) are the water-soluble organosiloxane compounds (7) and (1) described in the specification.
When the compounds (3), (15), (16) and (17) were replaced, almost the same effects as those of the exemplified compounds (1) and (3) could be obtained.

Example 3 Using the sample prepared in Example 1, in Experiment No. 1-8, the contact area with air per liter of stabilizing solution was 3 cm ² , 5c.
^{m 2, 8cm 2, 20cm 2} , 50cm 2, were carried out running processing experiment as 100cm ^2, but up to 50cm ² was exactly the evaluation is the same as the experiment 1-12.

In the case of 100 cm ² , it was the same except that the precipitation of sulfide was "△". (The contact area of a commonly used automatic processor is 10 to 20 cm ² / l.) As can be seen from the results, the present invention has excellent liquid storability even when the opening area is large. I understand.

Example 4 The hardener (H-2) in the film sample used in Experiment No. 1-14 of Example 1 was changed to the hardener shown in Table 6, and the other experiments of Example 1 were carried out. The experiment was conducted in the same manner as No. 1-14. The results are summarized in Table 6.

However, the occurrence of tar and the presence or absence of sticking did not change significantly depending on the type of hardener.
Excluded from.

[0207]

[Table 6]

[0208]

[Chemical 28]

From Table 6 above, it can be seen that when the vinyl sulfone type hardener is used in combination with the treatment method of the present invention, the effect of the object of the present invention is more excellently achieved.

Example 5 10 mg / m ^{2 of the} additives shown in Table 7 below were added to the film samples prepared in Experiment No. 1-13 of Example 1 to prepare experimental samples. Others were the same as those of Experiment No. 1-13 of Example 1. The results are summarized in Table 7.

[0211]

[Table 7]

From Table 7 above, when the treatment method of the present invention is used in combination with the compounds represented by the above general formulas [B-1] to [B-3], the effect of the present invention is more excellent. It turns out that the result is obtained.

Example 6 Experiment No. 1 of Example 1 was carried out by changing the addition amount of ammonium thiocyanate in the fixing solution of Example 1 as shown in Table 8.
An experiment similar to -13 was performed. Then, in the same manner as in Example 1, the fading rate of the dye after storage, the precipitation of sulfide, and the adhesion of scratch foreign matter after the treatment were evaluated by the same evaluation criteria as in Example 1. The results are shown in Table 8.

[0214]

[Table 8]

Example 7 The same running experiment as in Example 1 was carried out except that the following bleach-fixing solution was used instead of the bleaching solution and fixing solution of Example 1 and the processing steps were changed as follows.

Bleach-fixing solution and bleach-fixing replenishing solution Ammonium thiosulfate 240 g Diethylenetriamine pentaacetic acid Ammonium ferric acid 150 g Ammonium thiocyanate
50g ammonium sulfite
15 g thiourea 1 g 2-amino-5-mercapto-1,3,4-thiadiazole 2 g Make up to 1 liter with water and adjust to pH 7.0 with acetic acid and aqueous ammonia.

Processing step Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C. 775 ml Bleach fixing 3 minutes 38 ° C. 650 ml Stabilization 1 minute 38 ° C. Dry 1 minute 40-70 ° C.- (replenishment amount is light-sensitive material is the amount per 1 m ^2.) However, stabilization treatment is performed at 3 tank countercurrent, supplemented to the final tank of the stabilizing bath, was performed in a manner that overflow in front tank flows. The experiment was performed in the same manner as in Example 1 except that the film sample was included. The evaluation and the like were performed in the same manner as in Example 1. The results are shown in Tables 9-10.

[0218]

[Table 9]

[0219]

[Table 10]

From Tables 9 to 10 above, the replenishing amount of the stabilizing solution was 67 using the compound of the present invention (the compound represented by the general formula [F]).
It can be seen that when the amount is 0 ml / m ² or less, the effect of the present invention is excellent.

[0221]

EFFECTS OF THE INVENTION According to the present invention, it is possible not only to provide stable processing characteristics even when the replenishing amount to the stabilizing solution is low and to use the conventional formaldehyde-free, but also to suppress the fading of the dye. However, it prevents the precipitation of sulfides in the stabilizing bath, the generation of cotton-like floating substances and tar, and the adhesion of adhered substances to the wall of the stabilizing tank, and the occurrence of tar, scratches and foreign substances on the photosensitive material after drying. It is possible to provide a method for processing a silver halide color photographic light-sensitive material that can be reliably prevented.

Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material, comprising processing a silver halide color photographic light-sensitive material with a processing solution having fixing ability and then processing with a stabilizing solution. F] A method for processing a silver halide color photographic light-sensitive material, which comprises a compound selected from the compounds represented by the formula [F] and the replenishing amount of the stabilizing solution is 670 ml / m ² or less. General formula [F] [In the formula, Z represents an atomic group necessary for forming a carbocycle or a heterocycle, X represents an aldehyde group, and (R ₁ and R ₂ each represent a lower alkyl group),
n represents an integer of 1 to 4. ]