JPH05232663A - Treatment for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve storage property of a stabilizer, to suppress precipitation of sulfide and to prevent contamination by incorporating a specified compd. into a photosensitive material and incorporating a specified compd. into the stabilizer in a stabilizing bath. CONSTITUTION:The photosensitive material contains at least one kind of compd. expressed by formulae I-III and the stabilizer in a stabilizing bath contains at least one kind of compd. expressed by formula IV. In formula I, R1 is alkyl group, cycloalkyl group, aryl group, etc., and R2 and R3 are hydrogen atom, halogen atom, amino group etc., and M is hydrogen atom, alkali metal atom or ammonium group. In formulae II and III, R4 is hydrogen atom, alkali metal atom, etc., R5 and R6 are hydrogen atom, halogenated alkyl group, etc., R7 is hydrogen atom. halogen atom, etc., R8-R11 are hydrogen atom, halogen atom, hydroxyl group, etc. In formula IV, R1-R3 are hydrogen atom, alkyl group, or aryl group, 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 in a processing bath having a fixing ability and subsequently processed with a stabilizing solution without being substantially washed with water. The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which has improved storage stability, less scratches on the light-sensitive material during high-speed transport processing, and improved work environment safety.

[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 No. 2,
920,222 and S.R.Gold Basser (SRG
oldwasser), "Water Flow Rate in Immersion Washing of Motion Picture Film (Water Flow Rate in immersion-Washi
ng of Motion-picture Film) ”SMPTE. Vol.64, 24
8 to 253, May. (1955).

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 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, 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 yellow stain in the unexposed area, and the sulfurization The preventive effect was not sufficient.

Regarding formalin, in the United States, CIIT (Chemical Industry Association Toxicology Research Institute)
It has been announced that nasal cancer occurred in rats at 15 ppm,
NIOS (National Institute of Occupational Safety and Health), ACGI
H (Industrial Hygiene Government Specialist Council) 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, the regulation of deleterious substances and drugs, organic solvent poisoning regulation of labor safety law special regulations or regulation of household products, regulation of 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, for example, as a formalin substitute technique, a stabilizer (stabilizer) used in a stable process of rapid treatment in which water washing treatment is not substantially performed is disclosed in, for example, JP-A-63-63.
-244036, JP-A-62-27742 and JP-A-61-151538, it has been known to use hexamethylenetetramine compounds and hexahydrotriazine compounds. However, when these hexamethylenetetramine compounds and hexahydrotriazine compounds are used, although they have the effect of suppressing discoloration of the dyes, the fixing solution and the bleach-fixing solution are treated with a stabilizing solution without using washing water substantially. 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 a black precipitate of fine sulfide, which adheres to the photosensitive material to be processed and stains. I had a big problem that it would occur.

Further, in a large-sized automatic processor, there is a tendency that high-speed conveyance is performed due to the recent rapid processing, and under such a situation, pressure is applied to the lower turn roller portion of the automatic processor stabilizing tank, which causes scratches. It has been found that there is a problem that the occurrence of is likely to occur.

Further, in recent years, the amount of replenishment has tended to be reduced due to economic reasons and pollution reasons, and under these circumstances, the above problems become more serious failures.

[0015]

Therefore, the first object of the present invention is to improve the storage stability of the stabilizing solution, suppress the precipitation of sulfides, and prevent the generation of stains on the photosensitive material to be processed. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material that enables the above.

A second object is to provide a method for processing a silver halide color photographic light-sensitive material in which the occurrence of scratches on the light-sensitive material is improved even when a high-speed transport processing is carried out, and a third object. Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which can improve the safety of the working environment by removing or reducing formalin from the processing bath.

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

[0018]

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 a method of processing a silver halide color photographic light-sensitive material, a silver halide color photographic light-sensitive material is processed in a processing bath having a fixing ability and then directly processed in a stabilizing bath without passing through another processing bath. The photosensitive material contains at least one compound represented by the following general formulas [B-1] to [B-3], and the stabilizing solution of the stabilizing bath is represented by the following general formula [F]. It was achieved by a method of processing a silver halide color photographic light-sensitive material characterized by containing at least one compound.

[0020]

[Chemical 7]

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 carboxyl group (including a salt thereof) or a sulfo group (including a salt thereof). R ² and R ³ are each a hydrogen atom, a halogen atom, an amino group, a nitro group,
Hydroxyl group, alkoxycarbonyl group, carboxyl group (including its salt) or sulfo group (including its salt)
Represents. M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0022]

[Chemical 8]

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 alkylene, R
¹³ and R ¹⁴ each represent 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, a halogenated alkyl group. Represents an arylalkyl group, —R ¹⁵ —OR ¹⁶ or —CONHR ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁵
Both ¹⁶ and R ¹⁷ 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 hydroxyl group, an alkyl group, an amino group or a nitro group.

[0024]

[Chemical 9]

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.

As a preferred embodiment of the present invention, in the above processing method, 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 ₄ —O— (R ₅ —O) m—X ₁ , R ₄ represents a monovalent organic group, and R ₅ 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 ₁ or -PO ₃ M _2.
Here, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group.

[0029]

[Chemical 10]

In the formula, R ₆ is a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxy group,

[0031]

[Chemical 11]

R ₇ , R ₈ and R ₉ each represent a hydrogen atom or a lower alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group or a propyl group). The R ₇ , R ₈ and R ₉ may be the same or different. l _{1 to} l ₃ each represent an integer of 0 or 1 to 30, and p, q ₁ and q ₂ each represent an integer of 0 or 1 to 30. X ₂ and X ₃ are ethylene group, trimethylene group,

[0033]

[Chemical formula 12]

Represents

[0035]

[Specific Structure of the Invention]

The processing steps preferably used in the present invention are: color development → bleaching → fixing → stable color development → bleaching fixing → stable color development → bleaching → bleaching fixing → stable color development → fixing → bleaching fixing → stable black development → washing → reversal → color development → adjustment → bleaching → fixing → stability, but the steps of and are preferred. Further, in the present invention, a processing bath (liquid) having fixing ability
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 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 replenishing amount to the stabilizing bath is 670 cc./m ² of the light-sensitive material or less. More preferably 100cc. Or more and 500cc.
It is below, and particularly preferably 160 to 460 cc.

When the replenishing amount of the stabilizing solution exceeds 670 ml, the effect of the present invention is not remarkable, and the lower the replenishing amount is, the more remarkable the effect of the present invention is.

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.

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 6.0 to 11.0.
The range of -10.5, especially pH 7.5-10 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 cc./m ² or less from the effect of the object of the present invention, and more preferably 10 to 10
The range is 0 cc./m ² , with 20 to 70 cc./m ² being 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 are each a hydrogen atom or an optionally substituted alkyl group (for example, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, hydroxyethyl, n- Propyl, iso-propyl, chloromethyl, carboxyethyl etc.) or aryl group (eg phenyl, p-methoxyphenyl, p-hydroxyphenyl, m-sulfophenyl, m-carboxyphenyl etc.)
Represents an optionally substituted nitrogen-containing heterocycle (eg pyrrole, imidazole, piperidine, pyrazole, succinimide, triazole, tetrazole, thiadiazine, thiadiazoline, morpholine, piperazine, thiamorpholine, indole, indazole, benzimidazole, benzotriazole). , Pyrrolidine, pyrazolidine, hydantoin, urazole and the like).

Examples of the compounds represented by the general formula [F] are shown below.

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

[0049]

[Chemical 16]

[0050]

[Chemical 17]

[0051]

[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-1
4) (F-35), (F-36), (F-39), (F-45),
(F-55), (F-60), (F-65), (F-67), (F-6
8), (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 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.
It is in the range of 10 g.

Next, the compound of the general formula [I] will be further described. R ₄ in the general formula [I] is a monovalent organic group, for example, having 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Is an alkyl group (for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent of the aryl group is preferably 3 carbon atoms
~ 12 alkyl groups, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Such as undecyl or dodecyl. Examples of the aryl group include phenyl, tolyl, xynyl, diphenyl, naphthyl and the like, and phenyl or tolyl is preferable. The position at which the alkyl group is bonded to the aryl group,
It may be in ortho, meta or para position. R ₅ represents an optionally substituted ethylene group or an optionally substituted trimethylene group, and m represents an integer of 4 to 50. X ₁ is a hydrogen atom, --SO
₃ M ₁ or —PO ₃ M ₂ is shown, and M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom (Na, K or Li, etc.) or NH ₄ .

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

[0058]

[Chemical 19]

[0059]

[Chemical 20]

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 above general formula [II] will be shown.

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

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. Particularly, it prevents precipitation and causes scratches. Effective for prevention.

If it is less than 0.01 g / liter, the effect of the present invention is not obtained, and if it exceeds 20 g / liter, a large amount of the organosiloxane compound adheres to the surface of the photosensitive material, resulting in the promotion of stain.

The water-soluble organic siloxane compound of the present invention is disclosed, for example, in JP-A-47-18333, JP-B-55-51172, JP-B-51-37538, JP-A-49-62128 and US patent. It means a general water-soluble organic siloxane-based compound as described in, for example, Kakai No. 3,545,970.

These water-soluble organosiloxane compounds are U
It is generally available from CC (Union Carbide Co.), Shin-Etsu Chemical Co., Ltd., etc.

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 Society, London (1
964), by S. Chaberek AEMartell, "Organic Sequeste.
ring Agents ", Willey (1959), etc. mean a commonly known constant.

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 2 per liter of the stabilizing solution.
Good results are obtained in the range of 0 g.

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 per liter of stabilizing solution
It is preferably in the range of 0.001 to 1.0 mol, more preferably 0.
It is in the range of 002 to 0.2 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, 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 adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.) and the like can be added. Any combination of these compounds may be used as long as it is necessary to maintain the pH of the stabilizing bath and does not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. Absent.

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). And the metal substitution method (described in British Patent 1,353,805) and the like can be used. These silver recovery methods are particularly preferable when in-line silver recovery from a tank solution using an electrolysis method or an anion exchange resin further improves the suitability for rapid processing, but it is particularly preferable, but silver recovery from overflow waste solution may be carried out and recycled. ..

Further, the stabilizing solution is subjected to an ion exchange treatment, an electrodialysis treatment (see JP-A-61-28949) and a reverse osmosis treatment (JP-A-60).
-240153 and JP-A-62-254151).
Further, it is also preferable to use 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, a treatment with an ion exchange resin or a reverse osmosis membrane can be used alone or in combination. Is preferred. Regarding the ion exchange resin and reverse osmosis membrane, Open Technical Report 87-1984 and Open Technique 89-2051
It is described in detail in No. 1.

The salt concentration in the stabilizing solution is preferably 1000 ppm or less, more preferably 800 ppm or less.

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 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].

[0083]

[Chemical 25]

In the general formula [A], A _{1 to} A ₄ may be the same or different and each is —CH ₂ OH, —COOM ₃ or —PO ₃ M.
Represents ₄ M ₅ . M ₃ , M ₄ and M ₅ each represent a hydrogen atom, an alkali metal atom (eg sodium, potassium) or an ammonium group. X ₄ represents an alkylene group having 3 to 6 carbon atoms which may be substituted (for example, propylene, butylene, pentamethylene and the like). Examples of the substituent include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.

The preferred specific examples of the compounds represented by the above general formula [A] are shown below.

[0086]

[Chemical formula 26]

Other specific exemplified compounds 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-1
2) is mentioned.

As the ferric complex salt of the compounds (A-1) to (A-12), any of sodium salt, potassium salt and ammonium salt of these ferric complex salts can be 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.

Among the above compounds, 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 easily occurs 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 0.1 to 2.0 mol, and more preferably 0.15 to 1.5 mol / l, per liter of the bleaching solution.

The second organic acid represented by the above general formula [A]
When two or more kinds of iron complex salts and other ferric iron salts of organic acids such as ethylenediaminetetraacetic acid are used in combination, the effect of the present invention is more favorably exhibited by the above general formula [A].
It is preferable that the ferric iron complex salt of the compound represented by 70% or more accounts for 70% 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. Further, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one type or two or more types of the ferric salt may be used. Furthermore, one or more aminopolycaponic acids may be used. Further, 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
Effect on rapidity by containing imidazole and its derivative described in No. 31 or compounds represented by the general formulas [I] to [IX] described in the specification and at least one of these exemplified 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-63-17445, and exemplified compounds described on pages 22 to 25 of the specification, JP-A-53-95630 and JP-A-53-28426 The compounds described and the like can be used as well.

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 about 0.01 to 100 g, and more preferably 0.05 to 100 g per liter of the bleaching solution. 50 g, particularly preferably 0.05-15 g
Is.

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 using 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.
It is to be 5.5 or less. The pH of the bleaching solution is the pH of the processing tank during the processing of the silver halide light-sensitive material and can be clearly distinguished from the pH of the so-called replenishing solution.

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

The preferable replenishing amount of the bleaching solution is 500 cc. Or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, preferably 20 cc. To 400 cc., And most preferably 40 cc.
To 350 cc., And the lower the replenishment amount, the more remarkable the effect of the present invention.

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 processing replenisher storage tank, if desired, or a suitable oxidation is carried out. Agents such as hydrogen peroxide, bromate, excess acid salt and the like may be appropriately added.

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

Next, the fixing solution or the bleach-fixing solution in the fixing step adopted after the bleaching step preferably 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 / liter or more, more preferably 0.5 to 3.0 mol / liter.

The replenishing amount of the fixing solution or the bleach-fixing solution according to the present invention is preferably 900 cc./m ² of the light-sensitive material or less, more preferably ^{20 to} 750 cc / m ² of the light-sensitive material, particularly preferably 50 to 620 cc. Is. The pH of the fixer or the bleach-fixer according to the present invention is preferably in the range of 4-8.

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

Further, the addition amount of the compound represented by the general formula [FA] and the compound represented by the general formula (1) or (2) is in the range of 0.1 to 200 g per liter of the treatment liquid, and good results are obtained. Be done.

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. Furthermore, Japanese Patent Application No. 63-48931 specification 60
The compound represented by the general formula [B-1] or [B-2] described on the page is also included.

These sulfites and sulfite-releasing compounds are suitable as sulfite ions in an amount of at least 0.05 mol per liter of the fixing solution, preferably 0.08 to 0.65 mol / liter, more preferably 0.10 to 0.50 mol / liter. Particularly preferred. The range of 0.12 to 0.40 mol / liter 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 20 seconds, and particularly preferably 20 seconds to It is in the range of 3 minutes.

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 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 agitation means is added and the liquid is forcibly agitated, instead of the normal diffusion movement of the liquid. As a means for forcibly stirring the liquid, Japanese Patent Laid-Open No.
The means described in 64-222259 and JP-A 1-206343 can be adopted.

Further, in the present invention, a crossover time between each tank such as a fixing tank to a 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.

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.

[0117] 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 diameter when maximized (three significant figures, the least significant digit Rounds up to 4).

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of the projected image converted to a circular image of the same area in the case of grains having a shape other than spherical. is there.

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

Particularly preferred highly monodisperse emulsions are those in which the breadth of distribution defined by (standard deviation / average grain size) × 100 = width of distribution (%) is 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 Japanese Patent Application No. 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, the seed particles may be formed by an acidic method and further grown by an ammonia method having a high growth rate to grow the particles to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and silver ions and halides corresponding to the growth rate of silver halide grains as described in JP-A-54-48521 are used. It is preferable that the ions are sequentially injected and mixed simultaneously.

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
Disclosure No.308119 (hereinafter abbreviated as RD308119)
It is possible to use those described in. The following shows the locations of description.

[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 following are the places of description.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 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 Item Use of various couplers in the present invention And specific examples thereof are described in the above-mentioned Research Disclosure. Below are the relevant locations.

[Items] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D item VII C to G magenta coupler 1001 VII-D item VII C to 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 RD308119 XIV.

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

The light-sensitive material may be provided with auxiliary layers such as a filter layer and an 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 effects of the present invention are 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 compound represented by the following general formula [VS-I] is preferably used in the present invention.

General formula [VS-I] L- (SO ₂ -X ₅ ) m In the above general formula [VS-I], L is an m-valent linking group, and X ₅ is -CH = CH ₂ or-. CH ₂ CH ₂ Y, Y is a group capable of leaving in the form of HY by a base, for example, a halogen atom,
Sulfonyloxy group, sulfooxy group (including salt), 3
It represents a residue of a primary amine.

M represents an integer of 2 to 10, and when m is 2 or more, --SO ₂ --X ₅ may be the same or different.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (eg, alkylene, alkylidene, alkylidyne or the like or a group formed by combining these), an aromatic hydrocarbon group (eg, arylene or the like or these A group formed by bonding), -O-, -NR'- (R 'represents a hydrogen atom or preferably an alkyl group having 1 to 15 carbon atoms), -S-, -N <, -CO. An m-valent group formed by combining one or more bonds represented by —, —SO—, —SO ₂ — or —SO ₃ —, and when two or more —NR′— are included, they are R's of each other may combine to form a ring. The linking group L further includes those having a substituent such as a hydroxyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Specific examples of X ₅ 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.

[0141]

[Chemical 27]

Specific examples of compounds other than these include:
See Japanese Patent Application No. 2-274026, pages 122-128 (V
S-1), (VS-3), (VS-5), (VS-7), (VS-8), (VS-1
1), (VS-13) ~ (VS-21), (VS-23) ~ (VS-32), (VS-34) ~
(VS-53), (VS-55) to (VS-57) are listed.

The vinyl sulfone type hardener used in the present invention is, for example, aromatic compounds such as those described in German Patent No. 1,100,942 and US Pat. No. 3,490,911, JP-B-44-29622 and JP-A-44-29622. 47-25373, 47-24259, etc., heteroalkyl-bonded alkyl compounds, sulfonamides, ester compounds as described in JP-B-47-8736, JP-A-49- 1,435-tris [β- (vinylsulfonyl) -propionyl] -hexahydro-s-triazine as described in JP-B No. 24435, JP-B No. 50-35807, JP-A No. 51-44164, etc. And the compounds described in JP-A-59-18944 and the like.

These vinyl sulfone type hardeners are dissolved in water or an organic solvent to form a binder (eg gelatin).
To 0.005 to 20% by weight, preferably 0.02 to 10% by weight
Used. 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].

[0146]

[Chemical 28]

In the general formula [B-1], R ¹ is an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group,
It represents an alkoxycarbonyl group, an amino group, a carboxyl group (including its salt) or a sulfo group (including its salt). 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 carboxyl group (including a salt thereof) or a sulfo group (including a salt thereof). M represents a hydrogen atom, an alkali metal atom or an ammonium group.

[0148]

[Chemical 29]

In the general formulas [B-2] and [B-3],
R ⁴ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, -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 represent a hydrogen atom and a halogen, respectively. Atom, a halogenated alkyl group or an alkyl group, R ⁷ is a hydrogen atom, a halogen atom,
Alkyl group, aryl group, halogenated alkyl group, an arylalkyl group, -R ¹⁵ represents -OR ¹⁶ or -CONHR ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁶ and R ¹⁷ are both hydrogen atoms or an alkyl group , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
Are hydrogen atom, halogen atom, hydroxyl group,
It represents 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.

[0151]

[Chemical 30]

As a concrete example other than these, Japanese Patent Application No. 2-27
(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) and (B-).
-1-4) and (B-1-5).

The general formula (B-1) used in the present invention.
The compound represented by is per liter of the stabilizing solution of the present invention.
It is preferably used in 0.03 ~ 50g, more preferably 0.1
It is 2 to 10 g, and particularly preferably 0.15 to 5 g.

Specific examples of the compound represented by the above general formula [B-2] or [B-3] are shown below, but the invention is not limited thereto.

(B-2-1) 2-methyl-4-isothiazoline-
3-one (B-2-2) 5-chloro-2-methyl-4-isothiazoline-3-
On (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-
On (B-2-6) 2- (2-ethoxyethyl) -4-isothiazoline-
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-benzisothiazolin-3-one (B-3-4) 2-Ethyl-5-nitro-1,2-benzisothiazolin-3-one (B-3-5) 2-benzyl-1,2-benzisothiazoline-3-
On (B-3-6) 5-chloro-1,2-benzisothiazolin-3-one These exemplified compounds are described in US Pat. No. 2,767,172,
U.S. Patent No. 2,767,173, U.S. Patent No. 2,767,174, U.S. Patent No. 2,870,015, British Patent No. 84
No. 8,130, French Patent No. 1,555,416 and the like describe synthetic methods and application examples to other fields. There are also commercially available products such as Topside 300 (Permachem Asia Co., Ltd.), Topside 600 (Permachem Asia Co., Ltd.), Fineside J-700 (Tokyo Fine Chemical Co., Ltd.), Proxel GXL (ICI Co., Ltd.).

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, the 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 purposes or for movies. Can be applied to.

[0160]

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 0.18 UV Absorber (UV-1) 0.23 High Boiling Solvent (Oil-1) 0.18 Gelatin 1.2 Second Layer; First Intermediate Layer Gelatin 1.1 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) 0.72 Colored cyan coupler (CC -1) 0.07 DIR compound (D-1) 0.03 DIR compound (D-3) 0.02 High boiling point solvent (Oil-1) 0.60 Gelatin 1.1 4th layer; Medium speed red-sensitive emulsion layer Silver iodobromide emulsion (Average grain size) 0.7 [mu] m, AgI 8.0 mol%) 0.85 sensitizing dye (SD-1) 2.1 × 10 -5 ( mol / mole of silver) sensitizing dye (SD-2) 1.9 × 10 -4 Mole / mole of silver) Sensitizing dye (SD-3) 1.9 × 10 -4 ( mol / mole of silver) Cyan Coupler (C-2) 0.28 Colored cyan coupler (CC-1) 0.03 DIR compound (D-1) 0.01 High boiling point 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%) 1.5 Sensitizing dye (SD-1) 1.9x 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) 0.07 Cyan coupler (C-2) 0.08 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 layer Middle layer Gelatin 0.6 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 ( ^{D-4) 6.8 × 10 -5} ( mol / mole of silver) Sensitizing dye (SD-5) 6.2 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.54 Magenta coupler (M-2 ) 0.21 Colored magenta coupler (CM-1) 0.06 DIR compound (D-2) 0.017 DIR compound (D-3) 0.01 High boiling point solvent (Oil-2) 0.81 Gelatin 1.6 Eighth layer; Medium sensitivity green sensitive emulsion layer Iodour Silver halide 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 ( Sensitizing dye (SD-8) 1.5 × 10 ^-5 (mol / silver 1 mol) Magenta coupler (M-1) 0.07 Magenta coupler (M-2) 0.05 Colored magenta coupler (CM-1) 0.04 DIR compound (D-2) 0.018 High boiling point solvent (Oil-2) 0.30 Gelatin 0.9 9th layer; High-sensitivity green-sensitive emulsion layer Silver bromide emulsion (average grain size 1.0 .mu.m, AgI 8.0 mol%) 1.5 Sensitizing dye (SD-6) 1.2 × 10 -4 ( mol / mole of silver) Sensitizing dye (SD-7) 1.0 × 10 -4 (Mol / silver 1 mol) Sensitizing dye (SD-8) 3.4 × 10 ⁻⁶ (mol / silver 1 mol) Magenta coupler (M-1) 0.09 Magenta coupler (M-3) 0.08 Colored magenta coupler (CM-1) ) 0.04 High boiling point solvent (Oil-2) 0.31 Gelatin 1.1 10th layer; Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) 0.12 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 3.2 mol%) 0.6 Silver iodobromide emulsion (average grain size 0.7 µm) , AgI 8.0 mol%) 0.6 sensitizing dye (SD-9) 5.2 × 10 -4 ( mol / mole of silver) Sensitive dye (SD-10) 1.9 × 10 -5 ( mol / mole of silver) Yellow coupler (Y-1) 0.65 Yellow coupler (Y-2) 0.24 DIR compound (D-1) 0.02 High boiling solvent (Oil-2 0.18. Gelatin 1.2 Formalin scavenger (HS-1) 0.10 12th layer; high-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (average grain size 1.0 µm, AgI 8.0 mol%) 1.1 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) 0.08. 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 mol%) ) 0.5 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 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, polymerization average molecular weight: 10,000
And 1100000 two AF-2s were added.

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

[0165]

[Chemical 31]

[0166]

[Chemical 32]

[0167]

[Chemical 33]

[0168]

[Chemical 34]

[0169]

[Chemical 35]

[0170]

[Chemical 36]

[0171]

[Chemical 37]

[0172]

[Chemical 38]

The emulsion used in the above sample was a monodisperse 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.

Further, 10 mg / m ^{2 of the} additives shown in the following Tables 1 and 2 were added to the above light-sensitive materials to be used as an experimental film sample.

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 Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 400cc. Bleach 45 seconds 38 ± 2.0 ℃ 150cc. Fixation 1 minute 30 seconds 38 ± 2.0 ℃ 450cc. Stability 60 seconds 38 ± 5.0 ° C 600cc. Drying 1 minute 55 ± 5.0 ° C- * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

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

Color development replenisher replenisher Water 800cc. Potassium carbonate 35g Sodium hydrogen carbonate 3g Potassium sulfite 5g Sodium bromide 0.2g Hydroxylamine sulfate 3.1g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl ) Aniline sulfate 7.0g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid.

Bleaching solution Water 700 cc. 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Maleic acid 30 g Glacial acetic acid 20 g Succinic acid 15 g Water was added to 1 liter, Adjust to pH 4.4 with aqueous ammonia or glacial acetic acid.

Bleaching Replenisher Water 700 cc. 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g maleic acid 40 g glacial acetic acid 20 g succinic acid 20 g ammonia water or glacial acetic acid Adjust to pH 4.0 and add water to make 1 liter.

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

Fixing replenisher water 800 cc. Ammonium thiocyanate 150 g ammonium thiosulfate 180 g sodium sulfite 20 g ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizer and stable replenisher Water 900 cc. Additive (listed in Table 1 and Table 2) Listed in Table 1 and Table 2 Surfactant 3.0 g

[0185]

[Chemical Formula 39]

Ammonia water 1.0 cc. After adding water to make 1 liter, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The automatic developing machine used for continuous processing has a conveying speed.
A 20 m / min one was used. The stabilizing bath is composed of three countercurrent systems, each of which is equipped with a temperature control circulation filter and a replenishing port, and has the same functions as those of automatic processors for color negative films generally sold in the market. ing. In the continuous treatment, when the amount of replenishment to the stabilizing bath becomes the same as that of the stabilizing bath is expressed as one round, Table 1,
The combinations shown in Table 2 were performed up to 3 rounds. At the start of the continuous processing and at the end of the third round, the scratched state and the backside stain state of the processed film sample were observed. Furthermore, the occurrence of sulfidation in the second stabilizing tank was observed.

The above results are shown in Tables 3 and 4.

However, in the table, a mark ◯ means that no scratches or stains on the back surface of the film were observed, a mark was slightly recognized, and a mark x was clearly recognized, resulting in a failure. Further, the degree of sulfurization in the second stabilizing tank means that A is not present at all, B is slightly recognized, and C is clearly recognized.

[0190]

[Table 1]

[0191]

[Table 2]

[0192]

[Table 3]

[0193]

[Table 4]

From the above Tables 3 and 4, it can be seen that the treatment of the present invention improves the occurrence of scratches on the film, the backside stain and the sulfurization of the stabilizing tank, as compared with the comparative treatment.

Example 2 Using the light-sensitive material sample used in Example 1, continuous processing was carried out under the following processing conditions.

Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 400cc. Bleach fixing 4 minutes 45 seconds 38 ± 2.0 ℃ 730cc. Stability 1 minute 00 seconds 38 ± 5.0 ℃ 600cc. Dry 1 min 00 sec 55 ± 5.0 ° C- * Replenishment amount is the value per 1 m ² of the light-sensitive material.

The following color developing solution, bleach-fixing solution, stabilizing solution and its 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 cc. 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 cc. Ammonia After adjusting the pH to 6.5 with water or acetic acid, add water to make 1 liter.

Bleach-fixing replenisher Water 700 cc. Ethylenediaminetetraacetate iron (III) ammonium 120 g Diethylenetriamineiron (III) ammonium pentaacetate 150 g Ethylenediaminetetraacetic acid 2 g Sodium sulfite 30 g Ammonium thiosulfate 170 g Ammonium thiocyanate 150 g Ammonia water (25%) 15 cc. After adjusting the pH to 6.0 with aqueous ammonia or acetic acid, add water to make 1 liter.

Stabilizer and Stable Replenisher Each stabilizer and stable replenisher used in the experiment of Example 1 was used.

In continuous processing, the bleaching bath and fixing bath of the automatic developing machine of Example 1 were modified into one bath to obtain a bleach-fixing bath. Other continuous processing conditions and experimental conditions were the same as in Example 1,
The same evaluation as in Example 1 was performed.

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

Example 3 The hardener (H-2) in the film samples prepared in Experiment No. 1-4 of Example 1 was changed to a hardener as shown in Table 5 below, and the others were The experiment was conducted in the same manner as Experiment No. 1-4 of Example 1.

The results are summarized in Table 5.

[0206]

[Table 5]

[0207]

[Chemical 40]

From Table 5 above, it is understood that when the treatment method of the present invention is used in combination with a vinyl sulfone type hardener, the effect of the object of the present invention is better exhibited.

Example 4 The surfactant of the stabilizing solution used in Experiment No. 1-4 of Example 1 was changed to the one shown in Table 6 below, and the other experiments of Example 1 were carried out.
The experiment was conducted in the same manner as No. 1-4.

The results are summarized in Table 6.

[0211]

[Table 6]

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

From Table 6 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.

[0214]

According to the present invention, the storability of a stabilizing solution is improved, and the disadvantages of the precipitation of sulfide in a stabilizing bath and the resulting contamination of a light-sensitive material to be processed are improved.
It is possible to improve the phenomenon that the photosensitive material is scratched when a high-speed transport process is performed, and further it is possible to remove formalin, which has a problem in the safety of the working environment, from the processing solution without impairing the processing quality.

Claims (3)

[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. The photosensitive material contains at least one compound represented by the following general formulas [B-1] to [B-3], and the stabilizing solution of the stabilizing bath is represented by the following general formula [F]. A method for processing a silver halide color photographic light-sensitive material, which comprises at least one compound. [Chemical 1] [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 carboxyl group (including a salt thereof) or a sulfo 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 carboxyl group (including its salt) or a sulfo group (including its salt). M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] [Chemical 2] [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 ¹⁴
Each represents a hydrogen atom, an alkyl group or an arylalkyl group. ) Or an arylalkyl group, R ⁵ and R ⁶
Each represents a hydrogen atom, a halogen atom, 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,
Arylalkyl group, a -R ¹⁵ -OR ¹⁶ or -CONHR ¹⁷ (wherein R ¹⁵ represents an alkylene group, R ¹⁶ and R ¹⁷ both represent hydrogen atom or an alkyl ^{group.) R 8, R 9,} R ¹⁰ and R
Each ¹¹ represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an amino group or a nitro group. ] [Chemical 3] [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 method for processing 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]. .. Formula (I) in _{R 4 -O- (R 5 -O)} m-X 1 [wherein, R ₄ represents a monovalent organic group, R ₅ 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 ₁ or -PO ₃ M _2. Here, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. ] [Chemical 4] [In the formula, R ₆ is a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxy group, or R ₇ , R ₈ and R ₉ each represent a hydrogen atom or a lower alkyl group, and R ₇ , R ₈ and R ₉ may be the same or different. l _{1 to} l ₃ each represent an integer of 0 or 1 to 30, and p, q ₁ and q ₂ each represent an integer of 0 or 1 to 30. X ₂ and X ₃ are each an ethylene group, a trimethylene group, or Represents. ]