JPH05232661A - Treatment for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a processing method for a silver halide color photographic sensitive material by which storage property of a stabilizer can be improved, such problems as precipitation of sulfide in the stabilizer, contamination of a photosensitive material processed with that stabilizer, and generation of magenta stain for rapid continuous processing are avoided, and formalin can be removed from the processing bath or reduced in the amt. CONSTITUTION:The photographic material is processed with a processing liquid having a fixing ability and then treated in a stabilizer bath without using other processing baths. In this process, the crossover time between the processing bath having the fixing ability and the stabilizer bath is controlled to <=10sec, and the stabilizer bath contains a compd. expressed by formula. In formula, R1, R2 and R3 are hydrogen atom, alkyl groups or aryl groups, and X is nitrogen contg. heterocyclic group.

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, which is processed with a processing solution having a fixing ability and subsequently with a stabilizing solution without being substantially washed with water. While suppressing the precipitation that occurs inside,
The present invention relates to a processing method of a silver halide color photographic light-sensitive material capable of suppressing the fluctuation of a dye image and improving the safety of working environment.

[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.

However, in recent years, there has been a demand for a treatment process in which the amount of washing water is reduced and pollution measures are taken for economic reasons such as shortage of water resources, soaring sewerage charges and utility costs, and pollution reasons.

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. Golbasser (SRGoldw
Asser), "Water Flow Rate in Immersion-Washingof
Motion-picture Film) "SMPTE. Vol.64, 248-25
P. 3, May. (1955), etc.

There is also known a processing method in which a preliminary washing with water is provided immediately after the fixing bath to reduce the pollutant components contained in and attached to the light-sensitive material and entering the washing step, and to reduce the amount of washing water.

However, these techniques are not treatment methods that do not use washing water at all. Therefore, in recent years, when water resources are exhausted and the cost for washing is increasing due to price increase of crude oil and the like, it is becoming a serious problem.

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 formalin is generally used in the final processing step following the washing bath. Has been.

The formalin used in the stabilizing bath prevents the physical properties of the color photographic light-sensitive material, in particular, the occurrence of scratches on the surface of the color photographic light-sensitive material and the change in gradation due to the photographic light-sensitive material being gradually hardened over time. Has the effect of
Further, it is known that it is also effective for the deterioration of the stability of the dye image due to the unreacted coupler remaining in the color photographic light-sensitive material.

However, formalin, which is added to the stabilizing solution for the purpose of stabilizing the dye image, adheres to the light-sensitive material and forms an adduct with sulfite ions brought from the prebath (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. To solve these problems, it has been proposed to use an alkanolamine as shown in U.S. Pat.No. 4,786,583, but the use of the alkanolamine tends to adversely affect the unexposed yellow stain.
Moreover, the sulfidation preventing effect was not sufficient.

Regarding formalin, in the United States,
CIIT (Chemical Industry Association Toxicology Research Institute) formalin 15pp
It has been announced that nasal cancer occurred in the rat at m.
NIOS (National Institute of Occupational Safety and Health), ACGIH
(Industrial hygiene government specialists' meeting) also said that cancer may occur. Even in Europe, formalin is strongly regulated, and in West Germany, formalin has been regulated to 0.1 ppm or less in homes for 10 years.

Further, in Japan, as the harmfulness of formalin, due to the stimulating action on mucous membranes, deleterious substances and drugs are regulated, organic solvent poisoning regulation of labor safety law special regulation or regulation on household products, regulation on fiber and plywood. Since 1975, the Ministry of Health and Welfare has newly introduced formalin regulation for underwear and baby clothes, and a technology that can reduce formalin has been long sought.

Further, in recent years, as a formalin substitute technique, for example, Japanese Patent Application Laid-Open No. 63-2 has been used as a stabilizer (stabilizer) used in a stable process of rapid treatment in which water washing treatment is not substantially performed.
The use of hexamethylenetetramine-based compounds and hexahydrotriazine-based compounds has been known as described in JP-A-44036, JP-A-62-27742 and JP-A-61-151538. However, when these hexamethylenetetramine-based compounds and hexahydrotriazine-based compounds are used, although there is an effect of suppressing fading of the dyes, substantially no washing water is used, and when the fixer or the bleach-fixer is continuously treated with a stabilizer. In particular, when the processing solution is stored for a long period of time or when the number of processed sheets is small, thiosulfate is decomposed to generate black precipitates of fine sulfides, which adhere to the photosensitive material to be processed and cause stains. I had a big problem to do.

In order to deal with such a problem, Japanese Patent Laid-Open No. 3042/1990 discloses a washing bath in which a replenishing amount is 1000 ml or less per 1 m ^{2 of} a light-sensitive material to be processed after processing with a bath having a fixing ability containing thiosulfate. , Or in a method of continuously processing in a stabilizing bath, the occurrence of the above-mentioned precipitation and the processing of the light-sensitive material to be treated by treating the crossover time between the bath having a fixing ability and the washing bath or the stabilizing bath for 10 seconds or less. Techniques for preventing dirt have been proposed.

However, it has been found that even if the above method is used, the above-mentioned drawbacks cannot be completely prevented as long as formalin is used in the stabilizing solution. In particular, it becomes a big problem at the time of low replenishment processing and becomes a serious claim that cannot be ignored.

It has also been found that there is a problem that magenta stain occurs in the unexposed portion of the light-sensitive material when the rapid processing is continuously carried out by an automatic processor. It has been found that this defect is remarkable when the amount of treatment is small, that is, when the amount of replenishment to the stabilizing bath is small, the renewal rate of the stabilizing solution is low, and the amount of treatment is uneven.

Further, as long as formalin is used, the safety of the working environment cannot be improved, and the above requirements are still not satisfied.

[0017]

SUMMARY OF THE INVENTION The first object of the present invention is to improve the storage stability of a stabilizing solution, suppress the precipitation of sulfides, and prevent the light-sensitive material to be processed from being stained. Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material that enables the above.

A second object of the present invention is to provide a method of processing a silver halide color photographic light-sensitive material which makes it possible to prevent the generation of magenta stain in the light-sensitive material to be processed in the case of rapid and continuous processing.

A third object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which can improve the safety of working environment by removing formalin from the processing bath.

Other objects will become apparent in the detailed description which follows.

[0021]

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, in the processing method of a silver halide color photographic light-sensitive material according to the present invention, the silver halide color photographic light-sensitive material is processed in a processing bath having a fixing ability and then directly processed without passing through another processing bath. In the processing method of a silver halide color photographic light-sensitive material processed in a stabilizing bath, the crossover time between the processing bath having the fixing ability and the stabilizing bath is
A method of processing a silver halide color photographic light-sensitive material, characterized in that the stabilizing bath contains a compound represented by the following formula [F] for 10 seconds or less.

[0023]

[Chemical 7]

In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents a nitrogen-containing heterocyclic group.

Another preferred embodiment of the present invention is that the silver halide color photographic light-sensitive material contains a vinyl sulfonic acid type hardener.

Further, the stabilizing solution contains a compound represented by the following general formula [I] or [II].

In the general formula [I] R ₃ —O— (R ₄ —O) m —X ₁ , R ₃ represents a monovalent organic group, and R ₄ represents an ethylene group, a trimethylene group or a propylene group. , M represents an integer of 4 to 50. X ₁ represents a hydrogen atom, -SO ₃ M or -PO ₃ M _2.
Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0028]

[Chemical 8]

In the formula, R ₅ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group,

[0030]

[Chemical 9]

Represents R ₆ , R ₇ and R ₈ are each a hydrogen atom or a lower alkyl group (preferably having a carbon number of 1 to
4 is an alkyl group, such as a methyl group, an ethyl group and a propyl group. ), And R ₆ , R ₇ and R ₈ may be the same or different. l _{1 to} l ₃ are each 0
Or represents an integer of 1 to 4 and p, q ₁ and q ₂ are each 0
Alternatively, it represents an integer of 1 to 15. X ₂ and X ₃ are ethylene groups,
Trimethylene group,

[0032]

[Chemical 10]

Represents

Further, the silver halide color photographic light-sensitive material contains at least one compound represented by the following general formulas [B-1] to [B-3].

[0035]

[Chemical 11]

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.

[0037]

[Chemical formula 12]

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 Are hydrogen atom, halogen atom,
Represents a halogenated alkyl group or an alkyl group, R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, an arylalkyl group, —R ¹⁵ —OR ¹⁶
Or --CONHR ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁶ and R ¹⁷ both represent a hydrogen atom or an alkyl group), and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom. Represents a halogen atom, a hydroxy group, an alkyl group, an amino group or a nitro group.

[0039]

DETAILED DESCRIPTION OF THE INVENTION The processing steps preferably employed in the present invention are as follows: color development → bleach → fixing → stable color development → bleach fixing → stable color development → bleach → bleach fixing → stable color development → fixing → bleach fixing → Stable black-and-white development → washing → reversal → color development → adjustment → bleaching → fixing → stabilization, among which the preferred steps are and. That is, a processing bath (liquid) having fixing ability in the present invention
In that case, for example, bleach-fixing in the above processing step,
Alternatively, fixing and the like can be mentioned.

In the present invention, the crossover time is the time required for the photosensitive material to move from the liquid surface of the front bath to the liquid surface of the subsequent bath. In the present invention, the crossover time is 10 seconds or less, but the shorter the crossover time, the better, preferably 8 seconds or less, particularly preferably 6 seconds or less.

Therefore, the effect of the present invention is that the crossover time between the processing bath having the fixing ability and the stabilizing bath is 10 seconds or less, and in addition, the crossover between the stabilizing baths in the case of a multi-tank construction. It is preferable to set the time to 10 seconds or less in order to enhance the effect of the present invention.

Of course, the stabilizing bath may be composed of a single bath, in which case there is no crossover time between the respective baths constituting the stabilizing bath, and the effect of the present invention is that the processing bath has fixing ability. It is demonstrated only by setting the crossover time between the bath and the stabilizing bath to 10 seconds or less.

To reduce the crossover time to 10 seconds or less, there are a method of shortening the crossover distance and a method of increasing the conveying speed of the photosensitive material. However, if the conveying speed is increased, it is inevitable that a constant processing time is secured. The former method is preferable because the size of the developing machine is increased.

In the present invention, the stabilizing bath is preferably composed of a plurality of tanks, and the flow of the liquid connecting between the tanks is preferably a multi-stage countercurrent which is a direction opposite to the conveying direction of the photosensitive material, and particularly, Those configured with 2 to 4 tanks are preferable.

In the present invention, the preferable replenishment amount to the stabilizing bath is 920 ml or less per 1 m ² of the light-sensitive material, but an extreme reduction in the replenishment amount causes discoloration of the dye and precipitation of salts on the surface of the light-sensitive material after drying. Therefore, it is more preferably 100 ml or more and 800 ml or less.

Further specific setting of the replenishment amount depends on the tank configuration of the stabilizing bath, and it is possible to set a lower value as the number of tanks increases.

The pH of the stabilizing bath according to the present invention is preferably in the range of 5.5 to 11.0, and particularly 7 from the viewpoint of promoting the effect of the present invention.
The range of ˜10.5, especially pH 7.5 to 10 is preferred. The temperature is 15
The range is preferably 70 to 70 ° C, more preferably 20 to 55 ° C. Further, the stabilization bath treatment time according to the present invention is 12
It is preferably 0 seconds or less, more preferably 3 to 9
It is 0 second, most preferably 6 to 60 seconds.

In the present invention, it is preferable to provide a squeegee between the processing bath having a fixing ability and the stabilizing bath, and between the stabilizing baths to sufficiently drain the liquid, thereby saving the replenishment amount and preventing stains on the photosensitive material. Can be done more effectively.

In the present invention, the carry-over amount from the processing bath having fixing ability to the stabilizing bath is preferably 150 ml / m ² or less from the effect of the object of the present invention, more preferably 10 to 10
In the range of ^{0ml / m 2, 20~70ml / m} 2 it is particularly preferred.

Next, the compound represented by the general formula [F] used in the present invention will be explained.

In the general formula [F], R ₁ , R ₂ and R ₃
Is a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, hydroxyethyl,
n-propyl, iso-propyl, chloromethyl, carboxyethyl, etc.) or an aryl group (eg, phenyl, p-methoxyphenyl, p-hydroxyphenyl, m-sulfophenyl, m-carboxyphenyl, etc.), and X is substituted Or an unsubstituted nitrogen-containing heterocycle (for example, pyrrole, imidazole, piperidine, pyrazole, succinimide, triazole, tetrazole, thiadiazine, thiadiazoline, morpholine, piperazine, thiamorpholine, indole, indazole, benzimidazole, benzotriazole, pyrrolidine, pyrazine, hydantoin). , Urazole, etc.).

Specific examples of the compound represented by formula [F] will be given below.

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

Among the specific examples of the compound represented by the general formula [F], the more preferable compound is (F-1),
(F-2), (F-3), (F-8), (F-10), (F-
14), (F-35), (F-36), (F-39), (F-45),
(F-55), (F-60), (F-65), (F-67), (F-
68), (F-69), (F-72) and (F-74). 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 a stabilizing solution for a silver halide color photographic light-sensitive material. 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.

Specific examples of compounds represented by the general formula [I] are shown below.

[0064]

[Chemical 19]

As other specific exemplified compounds, Japanese Patent Application No.
2-274026, Nos. 63-65, (I-2), (I-
3), (I-4), (I-7) to (I-11), (I-13),
(I-15) to (I-19) can be mentioned.

These compounds represented by the above general formula [I] can be used in the stabilizing solution of the present invention in an amount of 0.1 to 40 g per liter, preferably 0.3 to 20 g.

Next, specific examples of the compound represented by the general formula [II] will be shown.

(Water-soluble organosiloxane compound)

[0069]

[Chemical 20]

Other specific examples Exemplified compounds include Japanese Patent Application No.
2-274026, (II-1), (II
-2), (II-5) to (II-7), (II-9) to (II-1)
1), (II-13), (II-14), (II-17).

The amount of the water-soluble organic siloxane compound having a polyoxyalkylene group added has a good effect when it is used in the range of 0.01 to 20 g per liter of the stabilizing solution, and particularly, precipitation prevention and yellow stain generation are achieved. Effective for prevention.

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

The water-soluble organic siloxane compound of the present invention is described in, for example, JP-A-47-18333, JP-B-55-51172, JP-B-51-37538, JP-A-49-62128 and US Pat.
It means a general water-soluble organic siloxane compound as described in 3,545,970.

These water-soluble organosiloxane compounds are U
It can be generally obtained from CC (Union Carbide Co.) and Shin-Etsu Chemical Co., Ltd.

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 o
f Metal-ion Complexes ”, The Chemical Society, Lon
don (1964), S.Chaberek AEMartell, “OrganicSe
Questering Agents ”, Willey (1959), etc.

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 preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per 1 liter of the stabilizing solution, and good results are obtained.

Ammonium compounds may be mentioned as preferred compounds to be added to the stabilizing solution. 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.

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, halides,
It can be supplied as an inorganic salt such as a hydroxide, a sulfate, a carbonate, a phosphate, an 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.

The stabilizing solution contains organic acid salts (citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjusting agents (phosphate, borate, hydrochloric acid, sulfate, etc.) and the like can be added. These compounds may be added in any combination so long as they maintain the pH of the stabilizing bath and do not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. I don't care.

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.

In the process of the present invention, silver may be recovered from the stabilizing solution. For example, an electrolysis method (described in French Patent 2,299,667), a precipitation method (described in Japanese Patent Laid-Open No. 52-73037, a description in German Patent 2,331,220), an ion exchange method (Japanese Patent Laid-Open No. 51-17114). Description, German Patent No. 2,548,237 specification) and metal substitution method (English Patent No. 1,353,805 specification) can be effectively used. For these silver recovery, in-line silver recovery from the tank liquid using an electrolysis method or anion exchange resin makes the rapid processing suitability even better,
Although it is particularly preferable, silver may be recovered from the overflow waste liquid and recycled.

Further, the stabilizing solution is treated with an ion exchange resin, electrodialysis (see JP-A-61-28949) or reverse osmosis (JP-A-61-28949).
60-240153 and JP-A-62-254151). 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. As a means of deionization treatment, C after washing water after treatment is used.
Any material may be used as long as it has a and Mg ions of 5 ppm or less, but it is preferable to use treatment with an ion exchange resin or a reverse osmosis membrane alone or in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Public Technical Report 87-1984 and Public Technical Report 89-20511. The salt concentration in the stabilizing solution is preferably 1000 ppm or less, more preferably 800 pp.
It is less than or equal to m.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

The color developing agent used in the color development processing step includes aminophenol compounds and p-phenylenediamine compounds, but in the present invention, p-phenylenediamine compounds having a water-soluble group are preferred.

Such a water-soluble group has at least one amino group of the p-phenylenediamine compound or on the benzene nucleus, and a specific water-soluble group is-(CH ₂ ) n-
CH ₂ OH,-(CH ₂ ) m-NHSO _2- (CH ₂ ) n-CH ₃ ,-(CH ₂ ) m-O-
_{(CH 2) n-CH 3} , - (CH 2 CH 2 O) nCmH 2 m +1 (m and n represent an integer of 0 or more, respectively.), - COOH group, those -SO ₃ H group and the like As.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-274026, specification 80.
(A-1) to (A-16) described on page 83.

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

The color-developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The color developing solution used in the color developing processing step is an alkali agent usually used in developing solutions such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or the like. Borax and the like can be included. Furthermore, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, hydroxylamine as a preservative, hydroxylamine derivative (eg diethylhydroxylamine), A hydrazine derivative (for example, hydrazinodiacetic acid), a sulfite, or the like can be included.

Furthermore, various antifoaming agents and surfactants are added.
Further, an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide may be appropriately contained.

The pH of the color developer is usually 7 or more, preferably about 9-13.

In the color developer, if necessary, as an antioxidant, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol,
Hydroxamic acid, bentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained.

In the color developing solution, various chelating agents can be used in combination as sequestering agents. For example, as the chelating agent, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, an organic phosphonic acid such as 1-hydroxyethylidene-1,1-diphosphonic acid, and an aminopolycarboxylic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid. Phosphonic acid,
Oxycarboxylic acid such as citric acid or gluconic acid, 2-
Examples thereof include phosphonocarboxylic acid such as phosphonobutane-1,2,4-tricarboxylic acid and the like, and folinic acid such as tripolyphosphoric acid or hexametaphosphoric acid and the like.

The preferable replenishment amount of the color developing solution in the continuous processing is 1,200 for the color negative film.
It is preferably 1.5 l or less per 0 m ² , more preferably 250 to 9
It is 00 ml, more preferably 300 to 700 ml.

The bleaching agent used in the bleaching solution or the bleach-fixing solution in the present invention is represented by a ferric iron complex salt of an organic acid represented by the following general formula [A] and A'-1 to A'-16 described later. A ferric iron complex salt of the exemplified compound may be mentioned.

[0098]

[Chemical 21]

In the general formula [A], A _{1 to} A ₄ may be the same or different and each is --CH ₂ OH, --COOM or --PO _3.
Represents M ₁ M ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. X has 3 carbon atoms
~ 6 represents a substituted or unsubstituted alkylene group.

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 , M and M
₁ and M ₂ each represent a hydrogen atom, an alkali metal atom (eg sodium, potassium) or an ammonium group.
X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.). A hydroxyl group and a C1-C3 alkyl group are mentioned as a substituent.

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

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

As the ferric iron complex salts of these compounds (A-1) to (A-12), sodium salt, potassium salt or ammonium salt of these second 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-mentioned compound examples, those particularly preferably used in the present invention are (A-1), (A-3),
(A-4), (A-5) and (A-9), and particularly preferred is (A-1).

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 0.15 to 1.5 mol / l, per liter of the bleaching solution.

In the bleaching solution or the bleach-fixing solution, preferred bleaching agents other than the iron complex salt of the compound represented by the general formula [A] are ferric complex salts of the following compounds (for example, ammonium, sodium, potassium, triethanolamine, etc.). The salt thereof is exemplified, but is not limited thereto.

(A'-1) Ethylenediaminetetraacetic acid (A'-2) Trans-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycine (A'-4) Ethylenediaminetetrakismethylenephosphonic acid (A ''-5) Nitrilotrismethylenephosphonic acid (A'-6) Diethylenetriamine pentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-8) Ethylenediaminedioltohydroxyphenylacetic acid (A'-9) Hydroxy Ethylethylenediaminetriacetic acid (A'-10) Ethylenediaminedipropionic acid (A'-11) Ethylenediaminediacetic acid (A'-12) Hydroxyethyliminodiacetic acid (A'-13) Nitrilotriacetic acid (A'-14) Nitrilo Tripropionic acid (A'-15) triethylenetetramine hexaacetic acid (A -16) The ethylenediaminetetraacetic propionic acid bleaching solution, the second of the formula (A) compounds represented by
The iron complex salt may be used in combination with one or more ferric iron complex salts of the compounds of A'-1 to A'-16.

When two or more ferric iron complex salts of organic acids are used in combination, the ferric iron complex salt of the compound represented by the general formula [A] is 70 or more from the viewpoint that the effect of the present invention can be better exhibited. % (Mol conversion) or more, more preferably 80% or more, particularly 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. And 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 salts may be used. Furthermore, one or two aminopolycarboxylic acids may be used.
You may use more than one kind. Further, in any case, the aminopolycarboxylic acid may be used in excess to form the iron (III) ion complex salt.

The bleach-fixing solution or bleaching solution containing the above iron (III) ion complex salt may contain a metal ion complex salt of cobalt, copper, nickel, zinc or the like other than iron.

The bleaching solution, the bleach-fixing solution and the fixing solution include imidazole and its derivatives described in JP-A No. 64-295258 or compounds represented by the general formulas [I] to [IX] described in the specification. And, by containing at least one of these exemplified compounds, it is possible to exert an effect on promptness.

In addition to the above-mentioned accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. The exemplified compounds described in JP-A-53-95630 and JP-A-53-28426 can also be used in the same manner.

These accelerators may be used alone or
Two or more kinds may be used together, and the addition amount is generally 1 liter of bleaching solution.
The range of about 0.01 to 100 g is preferable, 0.05 to 50 g is more preferable, and 0.05 to 15 g is particularly preferable.

When the 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, ethanol, It can also be dissolved in an organic solvent such as acetone and added.

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 bleach-fixing solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
Is.

The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank at the time of processing the silver halide photographic material, and can be clearly distinguished from the so-called replenishing solution pH.

To the bleaching solution or the bleach-fixing solution, a halide such as ammonium bromide, potassium bromide or sodium bromide is usually added and used. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained.

The preferred replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml. The more significant, the more remarkable the effect of the present invention becomes.

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

As the fixing agent used in the fixing solution or the bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is preferably at least 0.1 mol / l or more, more preferably 0.3 mol / l or more, and particularly preferably 0.5 mol / l or more when processing a color negative film. The content of thiosulfate is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when processing a color negative film.

The processing liquid having fixing ability of the present invention is disclosed in
It is preferable to add a compound represented by the general formula [FA] described in JP-A No. 64-295258, page 56, and the exemplified compounds thereof, and not only the effects of the present invention can be better exhibited but also a small amount of a light-sensitive material can be added. Another effect is that the sludge generated in the processing liquid having fixing ability is extremely small during processing over a period of time.

Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 to 200 g per liter of the treatment liquid.

The processing time with the bleaching solution and the fixing solution according to the present invention is arbitrary, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, particularly preferably 20 seconds to 20 seconds. It is in the range of 1 minute and 20 seconds. The processing time with the bleach-fix solution is preferably 4 minutes or less, more preferably 10 seconds to 2 minutes 20 seconds.

Providing forced agitation to the stabilizing bath of the treatment method of the present invention is a preferred embodiment of the present invention. The reason is that not only the effect of the object of the present invention is better achieved, but also the suitability for rapid processing is improved. Here, the forced liquid agitation means that the liquid is not normally diffused and moved, but that a stirring means is added and the liquid is forcibly agitated. As the forced stirring means, the means described in JP-A No. 64-222259 and JP-A No. 1-206343 can be adopted.

Further, in the present invention, when the crossover time between the color developing tank and the bleaching tank or the bleach-fixing tank is preferably within 10 seconds, more preferably within 7 seconds, the effect different from that of the present invention can be obtained. Effective against certain bleached fog.

Silver halide color photographic light-sensitive material (hereinafter
The silver halide grains used as "light-sensitive material" or "sensitive material" as necessary) are silver chloride, silver chlorobromide, silver iodobromide,
Any silver chloroiodobromide may be used, and silver iodobromide is preferably used in order to achieve the effects of the present invention.

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 there.

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.

When the silver halide emulsion contains grains having an average grain size / grain thickness of less than 5, the grain size distribution is preferably monodisperse in view of desilvering property.

The monodisperse silver halide emulsion means 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.

[0134] Here, the average particle size, the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size at which the maximum (three significant figures, the least significant digit Will be rounded to 4).

The grain size referred to here is the diameter of a spherical silver halide grain, and the diameter of a non-spherical grain when the projected image is converted into a circular image of the same area. Is.

The particle size can be obtained, for example, by enlarging the particle from 10,000 times to 50,000 times with an electron microscope, and measuring the particle diameter on the print or the area at the time of projection (measurement particle). It is assumed that the number is 1000 or more indiscriminately.) A particularly preferable highly monodisperse emulsion is (standard deviation / average grain size) × 100 = the width of the distribution defined by the width (%) is 20%. Is
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 (Japanese Patent Application Laid-Open No. 58-113934, Japanese Patent Application No. 59-170070).
No.) 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 may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow them to a predetermined size. 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 sequentially and simultaneously inject and mix halide ions with halide ions.

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

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 table below shows the locations.

[Item] [Page of RD308119] Iodine composition 993 IA Item Production method 993 I-A item and 994 E item Crystal habit Normal crystal 993 I-A Twin crystal 〃 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 places described in the table below are shown.

[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. The following table shows 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 Item Use of various couplers in the present invention And specific examples thereof are described in the above-mentioned Research Disclosure. The following table shows 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 RD108119 XIV.

In the present invention, the aforementioned 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 intermediate layer described in the above-mentioned RD308119 VII-K.

The light-sensitive material of the present invention is the above-mentioned 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, when a vinyl sulfone type hardener is used in the light-sensitive material, the effect of the present invention is more effectively exhibited.

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 following general formula [VS
-1] is preferably used in the present invention.

General formula [VS-I] L- (SO ₂ -X) m In the above general formula [VS-I], L is an m-valent linking group, and X is -CH = CH ₂ or -CH ₂ CH ₂ Y, Y represents a group capable of being eliminated in the form of HY by a base, for example, 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.

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 these A group formed by bonding with each other), -O-, -NR'- (R 'represents a hydrogen atom or an alkyl group preferably having 1 to 15 carbon atoms),-
S -, - N <, - CO -, - SO -, - SO 2 - or -SO ₃ - is the m-valent group formed by combining one or more of the bond represented by, -NR'- When two or more R's are included, their R's may combine to form a ring.
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.

Specific examples of X include -CH = CH ₂ or -CH ₂
CH ₂ Cl and the like are preferable.

Typical specific examples of the vinyl sulfone type hardener are shown below.

[0157] _{VS-2 H 2 C = CHSO} 2 (CH 2) SO 2 CH = CH 2 VS-4 H 2 C = CHSO 2 CH 2 OCH 2 SO 2 CH = CH 2

[0158]

[Chemical formula 24]

Other specific exemplified compounds are described in Japanese Patent Application No. 27404026, pages 122 to 128 (V
S-1), (VS-3), (VS-5), (VS-7), (V
S-8), (VS-11), (VS-13) to (VS-21), (VS
-23) to (VS-32), (VS-34) to (VS-53), (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 3,49.
Aromatic compounds as described in 0,911 and the like, alkyl compounds bonded with a hetero atom as described in JP-B-44-29622, 47-25373, 47-24259 and the like,
Sulfonamides and ester compounds as described in JP-B-47-8736 and 1,3,5-tris [β- (vinylsulfonyl) -propionyl] as described in JP-A-49-24435. -Hexahydro-s-triazine or Japanese Patent Publication Sho 50
-35807, alkyl compounds as described in JP-A-51-44164 and the like, compounds described in JP-A-59-18944 and the like.

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.

Next, the compounds represented by the general formulas [B-1] to [B-3] will be described.

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

[0164]

[Chemical 25]

Specific examples of other compounds include (B-1-4) described in Japanese Patent Application No. 2-274026, pages 130 to 132.
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.

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 compounds represented by the above general formulas [B-2] and [B-3] are shown below, but the invention is not limited thereto.

(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-isothiazoline
-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-
ON (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-
On these exemplified compounds, 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, British Patent 848,130, French Patent 1,555,416, etc. Synthetic methods and applications to other fields are described. 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.),
It is available under the trade name of Proxel GXL (ICI Corporation).

The compounds represented by the general formulas [B-1] to [B-3] are used in an amount of 0.1 to 500 mg, preferably 0.5 to 100 mg, per 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 motion picture color film and a television color film which are used for general use or for movies. It can be applied to materials.

[0172]

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 composition shown below 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 Third layer; 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) increase 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 point solvent (Oil-1) 0.64 Gelatin 1.2 4th layer; Medium-sensitive red-sensitive emulsion layer Silver iodobromide emulsion (average) Particle 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) ) Increase Dye (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) 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-sensitivity 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 x 10 ^-4 (Mol / 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 point Solvent (Oil-1) 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 / silver 1 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 silver iodobromide emulsion (average particle 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 stain 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 particle size 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 point 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 point solvent (Oil-1) 0.07 High boiling point 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 Lucari 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: 10000 and Mw: 110
0000 of two AF-2s were added.

The emulsion used in the above sample was a monodispersed surface low silver iodide-containing emulsion, which 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.

[0177]

[Chemical formula 26]

[0178]

[Chemical 27]

[0179]

[Chemical 28]

[0180]

[Chemical 29]

[0181]

[Chemical 30]

[0182]

[Chemical 31]

[0183]

[Chemical 32]

[0184]

[Chemical 33]

The color negative film produced as described above was photographed with Konica FS-1 (manufactured by Konica Corp.) and then continuously processed under the following conditions.

Treatment process Treatment process Treatment time Treatment temperature Complementary amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 536ml Bleach 45 seconds 38 ± 2.0 ° C 150ml fixation 1 minute 30 seconds 38 ± 2.0 ° C 830ml Stabilization 60 Second 38 ± 5.0 ℃ 830ml Dry 1 minute 55 ± 5.0 ℃ － * Replenishment amount is the value per 1m ² of light-sensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and their replenishers were used.

Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water is added to make 1 liter, and the pH is adjusted to 10.06 with potassium hydroxide or 20% sulfuric acid.

Color development replenisher liquid 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulphate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and adjust to pH 10.18 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 l, and ammonia water or glacial acetic acid was used.
Adjust to pH 4.4.

Bleaching Replenisher Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.0 with aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting pH to 6.2 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenishing Solution Water 900 ml Additive (Compound represented by General Formula F) Table 1 and Table 2

[0195]

[Chemical 34]

Ammonia water 1.0 ml Water was added to make 1 liter, and then ammonia water or 50% sulfuric acid was added.
Adjust to pH 8.5.

As the automatic processor used for continuous processing, a small Konica special automatic processor was used, and the crossover times from the fixing bath liquid level outlet to the stable bath liquid level inlet were set in Tables 4 and 5.
Those which can be changed as described in 1. were used. The stabilizing bath had a counter flow of 3 tanks. The processing time of each process of this small automatic processor is adjusted so that the length of the rack for transporting the film in each tank can be adjusted.

Each tank is provided with a temperature control circulation filter and a replenishing port, and has the same function as an automatic developing machine for color negative film generally sold in the market. The continuous treatment was performed up to 3 rounds with the combinations shown in Tables 1 and 2 when the amount of replenishment to the stabilizing bath was the same as that of the stabilizing bath as 1 round.

The unexposed film is processed at the start of the continuous processing and at the end of the third round, and the generation degree of magenta stain is measured by a densitometer and examined, and the formation of precipitate in the stabilizing bath and the processed film are visually determined. The degree to which dirt was generated was examined. The difference between magenta stain and that treated by washing with running water (3 l / min) instead of stabilizing treatment was determined as stain.

The results are summarized in Tables 4 and 5.

(Visual Evaluation Criteria) <Precipitation Occurrence> ○: No precipitation occurs △: Slight precipitation occurs in the stabilizing tank filter ×: Precipitation occurs on the entire surface of the stabilizing tank filter <Filter dirt> A: No filter dirt B: Several places Filter stains occur on C: Filter stains occur on many places

[0202]

[Table 1]

[0203]

[Table 2]

From Tables 1 and 2, it can be seen that the treatment of the present invention is superior in the degree of precipitation generation, film stain, and magenta stain generation as compared with the comparative treatment.

Example 2 The photosensitive material sample used in Example 1 was subjected to continuous processing under the following processing conditions.

Treatment process Treatment time Treatment temperature Complementary amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 536ml Bleach fixing 4 minutes 15 seconds 38 ± 2.0 ℃ 730ml Stability 1 minute 00 seconds 38 ± 5.0 ℃ 830ml Dry 1 minute 00 seconds 55 ± 5.0 ° C- * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleach-fixing solution, stabilizing solution and replenishing solution were used. The stabilizing tank was a three tank counter current system, and the replenisher was placed in the final tank.

Color developer and replenisher The same as used in Example 1.

Bleach-fixing solution Water 800 ml Ethylenediaminetetraacetate iron (III) ammonium 80 g Diethylenetriamine iron (III) pentaacetate ammonium 100 g Ethylenediaminetetraacetic acid 2 g Sodium sulfite 20 g Ammonium thiosulfate 150 g Ammonium thiocyanate 120 g Ammonia water (25%) 12 ml Ammonia water or Adjust to pH 6.5 with acetic acid and add water to add 1
Let l.

Bleach-fixing replenisher Water 700 ml Ethylenediaminetetraacetic acid iron (III) ammonium 120 g Diethylenetriamine iron (III) pentaacetate 150 g Ethylenediaminetetraacetic acid 2 g Sodium sulfite 30 g Ammonium thiosulfate 170 g Ammonium thiocyanate 150 g Ammonia water (25%) 15 ml Ammonia water Or adjust to pH 6.0 with acetic acid and add water to add 1
Let l.

Stabilizing Solution and Stable Replenishing Solution Each stabilizing solution and stable replenishing solution used in the experiment of Example 1 were used.

For continuous processing, the bleaching bath and the fixing bath of the automatic processor of Example 1 were modified into one bath to obtain a bleach-fixing bath.

An experiment was carried out by changing the crossover time from the bleach-fixing bath liquid level outlet to the stabilizing bath inlet in the same manner as in Example 1. Other continuous processing conditions and experimental conditions were the same as in Example 1, and the same evaluation as in Example 1 was performed.

As a result, almost the same results as in Example 1 were obtained.

Example 3 The hardener (H-2) in the film sample prepared in Experiment No. 1-3 of Example 1 was changed to a hardener as shown in Table 3 below, and Experiments were conducted in the same manner as Experiment No. 1-3 of Example 1.

The results are summarized in Table 3.

[0217]

[Table 3]

[0218]

[Chemical 35]

From Table 3 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 effects of the object of the present invention are more effectively exhibited.

Example 4 The stabilizer used in Experiment Nos. 1-15 of Example 1 was changed to the surfactant shown in Table 4 below, and the others were changed to Experiment N of Example 1.
It was carried out in the same manner as o.1-15.

The results are summarized in Table 4.

[0222]

[Table 4]

In the table, TEAC is triethylammonium chloride, DTMAC is dodecyltrimethylammonium chloride, LMTS is sodium lauroylmethyltaurate, and DBSS is sodium dodecylbenzenesulfonate.

From Table 4 above, the above-mentioned general formula [I] or [I]
It can be seen that, when the compound represented by I] is used in combination with the present invention, the effects of the present invention are better exhibited.

Example 5 The color negative film samples used in Experiment Nos. 1-4 of Example 1 were added with the compounds shown in Table 5 below so as to be 10 mg / m ² , and the others were included in Experiment No. 1 of Example 1. An experiment was performed in the same manner as in .1-4.

The results are summarized in Table 5.

[0227]

[Table 5]

From Table 5 above, the effect of the present invention can be obtained when the light-sensitive material used in the processing method of the present invention is used in combination with the compound represented by the above general formulas [B-1] to [B-3]. It turns out that it plays better.

[0229]

According to the present invention, the storage stability of the stabilizing solution is improved, the precipitation of sulfides in the stabilizing bath is suppressed, and the photosensitive material to be processed is contaminated. In this case, the generation of magenta stain is improved, and it is possible to remove formalin, which has a problem in the safety of the working environment, from the processing liquid without impairing the processing quality.

Claims (4)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material, which comprises treating a silver halide color photographic light-sensitive material with a processing bath having a fixing ability and then directly treating it with a stabilizing bath without passing through another processing bath. A silver halide color photograph characterized in that the crossover time between the processing bath having the fixing ability and the stabilizing bath is 10 seconds or less, and the stabilizing bath contains a compound represented by the following general formula [F]. Method of processing photosensitive material. [Chemical 1] [In the formula, R ₁ , R ₂ , and R ₃ each represent a hydrogen atom, an alkyl group, or an aryl group, and X represents a nitrogen-containing heterocyclic group. ] 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a vinyl sulfonic acid type hardener. 3. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein the stabilizing solution contains a compound represented by the following general formula [I] or [II]. Method. Formula (I) R ₃ -O- in _{(R 4 -O) m-X} 1 [wherein, R ₃ represents a monovalent organic group, R ₄ is an ethylene group,
It represents a trimethylene group or a propylene group, and m represents an integer of 4 to 50. X ₁ represents a hydrogen atom, -SO ₃ M or -PO ₃ M _2. Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] [Chemical 2] [In the formula, R ₅ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, or Represents. R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a lower alkyl group, and R ₆ , R ₇ and R ₈ may be the same or different. l _{1 to} l ₃ each represent an integer of 0 or 1 to 4, and p, q ₁ and q ₂ each represent an integer of 0 or 1 to 15. X ₂ and X ₃ are ethylene group, trimethylene group, Represents. ] 4. The silver halide color photographic light-sensitive material contains at least one of compounds represented by the following general formulas [B-1] to [B-3]. The method for processing a silver halide color photographic light-sensitive material as described in 2 or 3. [Chemical 5] [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 each represent a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including a salt thereof) or a sulfonic acid group (including a salt thereof). M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] [Chemical 6] [In the formula, R ⁴ represents a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, halogenated alkyl group, -R ¹² -OR ^13, -C
ONHR ¹⁴ (wherein R ¹² represents an alkylene group, and R ¹³ and R
Each of ¹⁴ represents a hydrogen atom, an alkyl group or an arylalkyl group. ) Or an arylalkyl group, R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, a halogenated alkyl group or an alkyl group, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a halogenated alkyl group. , An arylalkyl group, -R ¹⁵ -OR ¹⁶ or -CONHR
R ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁶ and R ¹⁷ both represent a hydrogen atom or an alkyl group), R
⁸ , R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amino group or a nitro group. ]