JPH06138600A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fog by processing the silver halide color photographic sensitive material containing a specified colored magenta coupler in a photographic constituent layer with a processing solution prepared by using the tablets of a processing agent for the photographic sensitive material. CONSTITUTION:The silver halide color photographic sensitive material has photographic constituent layers including blue-, green-, and red-sensitive silver halide emulsion layers on a support, and it contains in at least one of the photographic constituent layers at least one of the colored magenta coupler represented by formula I and it is processed with the processing solution prepared by using the tablets of the processing agent for use in the color photographic sensitive material. In formula I, R1 is a substituent: R2 is acylamino, sulfonamido, imido, carbamoyl, sulfamoyl, alkoxy, alkoxycarbonyl, or alkoxycarbonyl-amino; R3 is halogen or alkoxy; m is an integer of 0-5; and is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material which is easy to replenish and has less fog.

[0002]

2. Description of the Related Art Conventionally, a color light-sensitive material for photographing is usually subjected to color development, bleaching, fixing, washing and / or stabilizing steps after exposure, and a color paper light-sensitive material is subjected to color development, bleach-fixing after exposure ( (Bleaching, fixing), washing and / or stabilizing, and the black-and-white light-sensitive material is usually subjected to developing, fixing and washing after exposure.
Further, in the case of a reversal type photosensitive material, a reversal process is added to these processes.

In recent years, the processing of such a light-sensitive material is carried out by an automatic developing machine (hereinafter, also referred to as an automatic processor) to sequentially convey the processing solution containing the processing solution.

Conventionally, these processing solutions are composed of various components (hereinafter referred to as "part agents" or "part agents") so as to exhibit good performance during photographic processing. These parts agents are in contact with each other. When it is placed, it reacts and deteriorates for a long time, impairing its function as a photographic processing agent. In particular, since many treatment agents easily react with each other due to redox reaction, they are generally made into a kit by dividing them into one or two or more parts agents, and these are dissolved in a certain amount of water when used. Are used for.

The above-mentioned kitted parts agent is, for example,
Each is put in an inner container such as a bottle or a bag, and these are put together in an outer bag (for example, a cardboard box) and sold as a unit.

In recent years, there has been a strong demand for environmental protection and resource saving mainly in Europe and the United States, and a plastic container for a processing agent has become a particularly serious problem in photography. That is, although a plastic container for photography is cheap and convenient for storage and transportation and has excellent chemical resistance, an empty container is landfilled as industrial waste, discarded, or incinerated. The plastic container has almost no biodegradability, and when it is accumulated and incinerated, a large amount of carbon dioxide gas is generated, which causes a problem such as global warming. Further, as a user's problem, it has been pointed out that a large number of plastic containers are piled up in a narrow work space and the space is further narrowed.

Therefore, it is desired to develop a technology for reducing pollution, which does not substantially use plastic bottles, and tableting of a treating agent is being studied.

However, it has become clear that fog increases when a silver halide color photographic light-sensitive material is processed using a tableting processing agent.

[0009]

OBJECT OF THE INVENTION The object of the present invention is to process a silver halide color photographic light-sensitive material having less fog when a processing solution prepared by using a tableting processing agent for silver halide photographic light-sensitive material is used. To provide a method.

[0010]

The above object of the present invention is achieved by the following configurations.

1. A support has a photographic constituent layer containing a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, and at least one of the photographic constituent layers has the following general formula [CM -I], a silver halide color photographic light-sensitive material containing at least one of colored magenta couplers is treated with a processing solution prepared by using a tableting silver halide photographic light-sensitive material processing agent. A method for processing a silver halide color photographic light-sensitive material.

[0012]

[Chemical 2]

[Wherein R ₁ represents a substituent, R ₂ represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group or an alkoxycarbonylamino group,
R ₃ represents a halogen atom or an alkoxy group. m is 0
-5 and n represent the integer of 0-4. ] 2. 2. The method for processing a silver halide color photographic light-sensitive material as described in 1 above, wherein the tabletted silver halide photographic light-sensitive material processing agent contains at least one water-soluble lubricant. 3. 3. The method for processing a silver halide color photographic light-sensitive material as described in 2 above, wherein the water-soluble lubricant is at least one selected from alkali metal lauryl sulfate, alkali metal benzoate and polyethylene glycol.

The present invention will be described in detail below.

First, the tableting silver halide photographic light-sensitive material processing agent of the present invention will be described.

The photographic solid processing agent tableted in the present invention can be obtained by granulating raw material powders, then mixing and tableting. For example, JP-A-51-61837
No. 54-155038, No. 52-88025, British Patent 1,213,808
The method described in the specification of the issue can also be adopted.
At the time of tableting, a water-soluble lubricant is contained for the purpose of improving the strength and lubricity of the tablet.

The water-soluble lubricant may be added during granulation before tableting, may be added before granulation, or may be added after granulation.

In the present invention, the water-soluble lubricant is selected from boric acid, DL-leucine, fatty acid alkali metal salt, lauryl sulfate alkali metal salt, benzoic acid alkali metal salt, adipic acid, fumaric acid, sodium sulfate and polyethylene glycol. At least one selected from the group consisting of alkali metal lauryl sulfate, alkali metal benzoate, and polyethylene glycol is particularly preferable in order to effectively achieve the object of the present invention. .

The photographic solid processing agent tabletted in the present invention is very stable without causing deterioration of the processing capacity and discoloration due to a redox reaction during storage as seen in conventional liquid kits. In particular, when solidified, coating with a water-soluble binder has the effect that the properties of the raw material of the treatment agent do not change for a very long period of time. Examples of the water-soluble binder include polyvinyl alcohol-based, methyl cellulose-based, polyethylene oxide-based, starch-based,
Examples thereof include polyvinylpyrrolidone-based, hydroxypropylcellulose-based, pullulan-based, dextran-based and gum arabic-based binders.

Also, during storage, transportation and handling to prevent atmospheric humidity such as high humidity, rain and fog and damage from accidental contact with water by water splashes or wet hands,
The photographic processing agent is preferably packaged in a moisture-proof packaging material.

As the moisture-proof packaging material, a film having a film thickness of 10 to 150 μm is preferable, and the moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene or polypropylene, or kraft paper, wax paper or moisture resistant moisture resistant polyethylene. Cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and metal foils such as aluminum, preferably at least one selected from metallized polymer film, and these are also It may be the composite material used.

However, in the present invention, the moisture-proof packaging material is more preferably a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastics include those made of natural polymers, polymers produced by microorganisms, synthetic polymers having good biodegradability, and blends of biodegradable natural polymers with plastics. As a concrete example,
For example:

Examples of natural polymers include polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and derivatives thereof. Microorganism-produced polymers include PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate). "Biopol" (manufactured by ICI), which has a biodegradable property as a component, and biodegradable synthetic polymers such as microbial-produced cellulose are polyvinyl alcohol, polycaprolactone, etc., or their copolymers or mixtures. Starch and cellulose are examples of natural polymers with good biodegradability that are used in the blending of biodegradable natural polymers into plastics. Examples thereof include a group that is excited and is linked to cleavage in the main chain.
Specifically, there is the introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added to accelerate disintegration.

Further, in addition to the polymers listed above, those having two functions of photodegradability and biodegradability at the same time are also preferably used.

Regarding such degradable plastic,
`` Science and Industry '' Vol. 64, No. 10, pp. 478-484 (1990),
The materials generally described in "Functional materials", July 1990, pp. 23-34, can be used. Also, Biopol
(Made by ICI), Eco (Made by Union Carbide), Eco
lite (Eco Plastic), Ecostar (Eco Star) (St. Lawrence Starch), Knuckle P
A commercially available degradable plastic such as (manufactured by Nippon Unicar Co., Ltd.) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5
g · mm / m ² 24 hours or less.

Specific methods for dissolving the solid treating agent include a method of dissolving the solid treating agent in water once stored in a replenishing tank and the like, and a method of replenishing the treating tank, and a method of directly adding to the treating tank and dissolving. In the former case, a replenishment tank is required separately from the processing tank, so the latter method is preferable in that it can be dissolved without taking up space.

In the present invention, in order to supply the tableted solid photographic processing agent to the automatic developing machine, the area of the processed photosensitive material is integrated by the detecting device attached to the photosensitive material insertion port of the automatic developing machine. When a certain unit is reached, a predetermined amount of the replenishing treatment agent is replenished directly to the treatment tank section of the automatic developing machine in a solidified amount or one or several units.

The area detecting device for the photosensitive material to be processed may be any of the conventionally used microswitch system, infrared system and ultrasonic system, as long as the photosensitive material to be processed can be reliably detected.

Regarding the method of replenishing the solidified photographic processing agent for tablets of the present invention, the processing tank of the developing machine, for example, the processing solution tank, the processing solution circulation system or the temperature control tank, the processing solution filtration filter section, etc. Direct replenishment gives good results.

When the tableted solid processing agent for photographic use is used, it is possible to freely change the size and shape of the solid photographic processing agent according to the unit to be supplied. Units that receive signals transmitted from the area detection device for the photosensitive material that is processed in predetermined amounts through the replenishment mechanism from the top of the processing liquid tank, processing liquid circulation system, temperature control tank, processing liquid filtration filter unit, etc. It is preferable to replenish each time.

Further, the solid photographic processing agent replenishing section prevents the scattering of processing solution due to the temperature of the processing tank of the developing machine, the temperature of the outside air, and the photosensitive material to be processed from coming into contact with the solid photographic processing agent before replenishment. It is more preferable that the device is devised.

Next, the tabletted solid photographic processing agent of the present invention can be applied to any processing solution for processing a silver halide photographic light-sensitive material. For example, general black-and-white developing solution, first developing solution for reversal film, squirrel infectious developing solution, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, stop solution, hardening solution, stabilizing solution, fog. Examples of the liquid include liquids and toning liquids, but are not limited thereto.

The tableted solid processing agent for photographic use of the present invention includes all halogens such as color film, color photographic paper, reversal film, general-purpose black and white film, X-ray film, printing lith film and micro film. It can be used for processing a silver halide photographic light-sensitive material.

The processing liquid in which the tabletted solid photographic processing agent of the present invention is dissolved and the processing method using the processing liquid will be described below.

The treatment steps adopted in the preferred treatment method include, but are not limited to, the following steps.

Color development → bleach-fixing → stable Color development → bleaching → fixing → stable color developing → bleaching → bleach fixing → stable color developing → bleach fixing → fixing → stable color developing → fixing → bleach-fixing → stable color developing → bleaching → Bleach-fixing → fixing → stability In the present invention, at least one processing solution in the processing step may be a processing solution prepared using a tableting silver halide photographic light-sensitive material processing agent, and others. The treatment liquid of (1) may be prepared with an ordinary replenisher or a powdery or granular treatment agent.

The processing liquid used in the above processing step will be described below. In the following description, the processing liquid obtained by dissolving the solid photographic processing agent is referred to as a tank liquid or simply a processing liquid.

As the color developing agent used in the color developing processing solution, a p-phenylenediamine compound having a hydrophilic group is preferably used because the effect of the present invention is satisfactorily achieved and fogging is less likely to occur.

The p-phenylenediamine-based compound having a hydrophilic group is compared with a p-phenylenediamine-based compound having no hydrophilic group such as N, N-diethyl-p-phenylenediamine.
It has advantages that the light-sensitive material is not contaminated and that the skin is not easily rashed. The hydrophilic groups include those having at least one on the amino group or benzene ring of p- phenylenediamine compound, as a specific hydrophilic _{group, - (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) _n C _m H _{2m + 1} ,-(CH ₂ ) _m-
Preferred examples include CON (C _m H _{2m + 1} ) ₂ , (m and n each represent an integer of 0 or more), —COOH, —SO ₃ H and the like.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169, 26 to 31.
(C-1) to (C-16) described on pages, JP-A-61-61
-289350, pages 29-31 (1)-(8),
And JP-A-3-246543, pages 5-9 (1).
To (62), particularly preferably, the exemplified compounds (C-1), (C-3) described in Japanese Patent Application No. 2-203169,
Exemplified compound (2) described in JP-A-61-289350 and exemplified compound (1) described in JP-A-3-246543 may be mentioned.

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

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

When the compounds of the following general formulas [I] and [II] are contained in the color developing tank solution, not only the effects of the present invention are better exhibited but also the fog generated in the unexposed areas is small. The effect also occurs.

General formula [I] (R ₁ ) (R ₂ ) N- (OH) In the general formula [I], R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group or R '(C = O). )-, R ₁ and R ₂ are not hydrogen atoms at the same time.
The alkyl groups represented by R ₁ and R ₂ may be the same or different and are preferably alkyl groups having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group.

R'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and aryl group of R ₁ , R ₂ and R ′ include those having a substituent, and R ₁ and R
₂ may combine to form a ring, for example, piperidine,
Heterocycles such as pyridine, triazine and morpholine may be formed.

[0048]

[Chemical 3]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₄ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group. It represents a substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group. Examples of the heterocyclic group include those having a 5- or 6-membered ring, which are composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅ is -CO -, - SO ₂ - or - (C = NH) - represents a divalent group selected from, n is 0 or 1. Especially n = 0
In this case, R ₁₄ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ₁₃ and R ₁₄ may together form a heterocyclic group.

Specific examples of the hydroxylamine compound represented by the above general formula [I] are described in US Pat. No. 3,287,125.
Although described in No. 3,329,3034 and No. 3287124,
Particularly preferred specific exemplified compounds include Japanese Patent Application No. 2-2031
(I-1) to (I-39) described on page 36 to 38 of the specification of 69 and (1) to (5) described on page 3 to 6 of the specification of JP-A-3-33845.
3) and (1) described in JP-A-3-63646, pages 5-7.
~ (52).

Specific examples of the compound represented by the above general formula [II] include (B-1) to (B-33) described in Japanese Patent Application No. 2-203169, pp. 3-33846, (1) to (56) described on pages 4 to 6 of the specification.

The compounds represented by the general formula [I] or the general formula [II] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluene sulfonate, oxalate, phosphate, acetate and the like.

A slight amount of sulfite can be used as a preservative in the color developing tank solution, and a buffer can be used.

Further, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-9
No. 019 and U.S. Pat. No. 3,813,247, thioether compounds, JP-A-52-49829 and JP-A-50-15554, p-phenylenediamine compounds, JP-A-50-137726.
JP-B-44-30074, JP-A-56-156826 and 52-43
Quaternary ammonium salts represented by 429, US Pat.
P-aminophenols described in 10,122 and 4,119,462, U.S. Patents 2,494,903, 3,128,182 and 4,230,79
No. 6, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,48
Amine compounds described in 2,546, 2,596,926 and 3,582,346, etc., Japanese Patent Publication Nos. 37-16088, 42-25201, U.S. Patents 3,128,183, 41-11431, 42-23883 and U.S. If necessary, polyalkylene oxide represented by Patent 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

It is preferable that the color developer contains substantially no benzyl alcohol. Substantially means not more than 2.0 ml per liter of color developing tank solution, and more preferably not containing at all. When it is not substantially contained, fluctuations in photographic characteristics during continuous processing, especially increase in stain are small, and more preferable results are obtained.

Chlorine ions and bromine ions are preferably contained in the color developing tank solution for the purpose of preventing fog. The chlorine ion content is preferably 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter, more preferably 4 × 10 ^-2 to 1 ×.
It is 10 ^-1 mol / liter. Chloride concentration is 1.5 × 10
^{If it is} more than ^-1 mol / liter, it is not preferable to delay the development and obtain a high maximum density rapidly. Also, 1.0 × 10 ^-2
If it is less than mol / liter, stain is generated, and further, fluctuation in photographic properties (particularly minimum density) due to continuous processing becomes large, which is not preferable.

The content of bromide ion is preferably 3.0.
The concentration is x10 ^-5 to 1 x 10 ^-3 mol / liter, and more preferably 5.0 x 10 ^{-5 to} 5.0 x 10 ^-4 mol / liter. When the bromine ion concentration is higher than 1 × 10 ^-3 mol / liter, development is delayed, the maximum concentration and sensitivity are lowered, and when the bromine ion concentration is lower than 3.0 × 10 ^-5 mol / liter, stain is generated, and continuous processing is performed. It is not preferable because it causes photographic characteristic fluctuation (especially minimum density).

When added directly to the color developer, sodium chloride, potassium chloride, chlorine chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Examples thereof include manganese chloride and calcium chloride, of which sodium chloride and potassium chloride are preferable. Examples of the bromide ion supplying substance include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Of these, preferred are potassium bromide and sodium bromide.

Further, these may be supplied in the form of a counter salt of the optical brightening agent added to the color developing solution.

If desired, the color developer used in the present invention may contain any antifoggant in addition to chlorine ion and bromine ion. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine, adenine Representative examples of such nitrogen-containing heterocyclic compounds can be given.

The color developer used in the present invention preferably contains a triazinyl stilbene type optical brightening agent from the viewpoint of the effect of the object of the present invention.

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

[0063]

[Chemical 4]

Detailed description of the general formula [III] is described in Japanese Patent Application No. 2-178.
It has the same meaning as the description of the general formula [E] described on pages 73 to 75 of the specification of 833.

Illustrative compounds of the general formula [III] include, for example, III-1 to 45, Japanese Patent Application No. 2-178833, pages 76 to 82, E-1 to 45, and the like.

The triazinyl stilbene whitening agent can be synthesized by the usual method described in, for example, "Fluorescent Whitening Agent" edited by Chemical Industry Association, page 8 (issued in August 1976).

Among the exemplified compounds, III-4, 24, 34, 35, 36, 37 and 41 are particularly preferably used.

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

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include, for example,
N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride, etc. It is known that the addition amount is usually
0.01 to 1.0 g / liter is preferable.

Furthermore, various other additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

For the color developing tank liquid, Japanese Patent Application No. 2-2404
From the viewpoint of effectively achieving the object of the present invention, the addition of the chelating agent represented by the following general formula [K] and its exemplified compounds K-1 to K-22 described in No. 00, pp. 69-74, is effectively achieved. preferable.

[0072]

[Chemical 5]

Among these chelating agents, K-
2, K-9, K-12, K-13, K-17, and K-19 are preferably used, and the effects of the present invention are particularly good when K-2 and K-9 are added to the color developer. To play.

The amount of these chelating agents added is preferably 0.1 to 20 g, and more preferably 0.2 to 8 g, per liter of the color developing tank solution.

Furthermore, the color developing tank liquid contains anions,
Cationic, amphoteric and nonionic surfactants can be contained. The color developing tank solution may have an arbitrary pH range, but preferably has a pH range of 9.9 to 10.9.

In the color negative processing, the replenishing amount of the color developing solution in the continuous processing is preferably 1.5 liters or less per 1 m ² of the light-sensitive material, more preferably 250 to 900 ml.
And more preferably 300 to 700 ml. In color paper processing, the amount is 120 ml or less, and more preferably 20 to 100 ml, per 1 m ² of the light-sensitive material.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution will be described. In the following description, various compounds contained in the solid processing agent may be described as components contained in the processing liquid, but they also mean components contained in the solid processing agent unless otherwise specified. .

The bleaching agent used in the bleaching solution and the bleach-fixing solution is not particularly limited, but it is preferable to use the compound represented by the following general formula [IV].

[0079]

[Chemical 6]

[In the formula, 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,
M ₁ and M ₂ each represent a hydrogen atom, an alkali metal or another cation (for example, an alkali metal such as sodium or potassium, or ammonium). X is a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (for example, propylene,
Butylene, pentamethylene). ] Specific preferred examples of the compound represented by the general formula [IV] are shown below, but the invention is not limited thereto.

IV-1 (HOOC-CH ₂ ) ₂ N- (CH ₂ ) ₃ -N (CH ₂ -COOH) ₂ IV-2 (HOOC-CH ₂ ) ₂ N- (CH ₂ ) ₄ -N (CH the _{2 -COOH) 2 IV-3 (} HOOC-CH 2) 2 N-CH 2 -C (CH 3) 2 -CH 2 -N (CH 2 -COOH) 2 other specific exemplified compounds, Japanese Patent Application No. (A-2) and (A-3) described on pages 89 to 90 of the specification of Hei 2-274026.
(A-5) to (A-8) and (A-10) to (A-12). Among them, IV-1 is preferable.

These IV-1, IV-2, IV-3, (A-
2), (A-3), (A-5) to (A-8), (A-1
The ferric complex salts of the compounds of 0) to (A-12) can be used in the form of sodium salt, potassium salt or ammonium salt.

The compound represented by the general formula [IV] is preferably contained in the range of 0.1 mol to 2.0 mol per liter of the bleaching solution, more preferably in the range of 0.15 to 1.5 mol / liter. It is preferably contained in the range of 0.05 mol to 1.0 mol per liter, more preferably in the range of 0.1 to 0.5 mol / liter.

In the present invention, in the bleaching solution or the bleach-fixing solution, a ferric complex salt of the compound represented by the above general formula [IV] and a ferric complex salt of an organic acid such as ethylenediaminetetraacetic acid are used in combination as a bleaching agent. In this case, the effect of the present invention is satisfactorily achieved. In that case, it is preferable that the iron (III) complex salt of the compound represented by the general formula [IV] accounts for 70% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably 95% or more. Is.

In the present invention, it is preferable that the ammonium ion in the bleaching solution or the bleach-fixing solution is 50 mol% or less of all cations in order to exert the effects of the present invention. Further, the effect is remarkable when the ammonium ion content is 30 mol% or less of all cations.

In the present invention, the bleaching solution and the bleach-fixing solution include imidazole and its derivatives described in JP-A-64-295258 or the general formulas [I] to [IX] described in the specification.
By containing the compound represented by and at least one of these exemplified compounds, it is possible to exert an effect on rapidity.

In addition to the above-mentioned accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and JP-A-6-123456
The exemplified compounds described on pages 22 to 25 of the specification of 3-17445, the compounds described in JP-A Nos. 53-95630 and 53-28426, and the like can also be used in the same manner. In the bleaching solution or bleach-fixing solution, in addition to the above, halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents,
An antifoaming agent or a surface active agent may be contained.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 to 5.5, and the bleach-fixing solution is preferably used in the range of pH 5.0 to 9.0, more preferably pH.
Used in the range of 6.0 to 8.5. The pH referred to here is the pH of the processing tank during processing of the silver halide light-sensitive material.

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

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air may be blown or oxygen may be blown in the treatment bath and the treatment replenisher storage tank, if desired, or a suitable treatment is carried out. An oxidizing agent such as hydrogen peroxide, bromate, persulfate or the like may be added as appropriate. or,
A member having a high oxygen permeability, such as silicone rubber, can be used as a pipe of an automatic processor.

Next, as the fixing agent used in the fixing solution,
Although not particularly limited, thiocyanates and thiosulfates are preferably used, but it is preferable to use thiosulfates in order to exert the effects of the present invention well.

The content of the fixing agent is at least in the tank liquid.
0.1 mol / liter is preferable, and 0.3 to 4 is more preferable.
Mol / liter, particularly preferably 0.5 to 3 mol / l
It is 1 liter, particularly preferably 0.6 to 2.0 mol / liter.

In the present invention, it is preferable that the ammonium ion content in the fixing solution is 50 mol% or less of all cations in order to exert the effects of the present invention. Further, the effect is remarkable when the ammonium ion content is 30 mol% or less of all cations.

In addition to the fixing agent, the fixing solution may contain one or more pH buffer agents composed of various salts. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Further, compounds known to be added to ordinary bleach-fixing solutions such as alkylamines and polyethylene oxides can be added as appropriate.

In the present invention, silver can be recovered from a bleaching solution, a fixing solution or a bleach-fixing solution by a known method.

A bleaching solution, a fixing solution or a bleaching-fixing solution can be prepared by using the following general formula [F
The compound represented by A] and this exemplified compound may be added.

[0097]

[Chemical 7]

The compound represented by the general formula [FA] described in the above specification is described in US Pat. No. 3,335,161 and US Pat.
It can be synthesized by a general method as described in 0,718. These compounds represented by the above general formula [FA] may be used alone or in combination of two or more kinds.

Further, the compounds represented by the general formula (1) or (2) described on pages 5-10 of WO 91/08517 may be used.

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

Further, it is also preferable to add a compound represented by the general formula [FA] or [FB] described in Japanese Patent Application No. 2-41549 and its exemplified compounds, so that the effects of the present invention can be better exhibited. Alternatively, it is preferable for achieving ammonia-free conversion.

In the present invention, the replenishing amount of the fixing solution is preferably 900 ml or less, more preferably 20 ml, per 1 m ² of the light-sensitive material.
The temperature of the fixing solution, which is ˜750 ml, is preferably 20 ° C. to 50 ° C., preferably 25 ° C. to 45 ° C.

The pH of the fixing solution is preferably in the range of 4.0 to 8.0.

The processing time with the bleaching solution and the fixing solution is arbitrary, but is preferably 6 minutes and 30 seconds or less, more preferably 10 seconds to 4 minutes and 20 seconds, and particularly preferably 20 seconds to 3 minutes.
It is in the range of 20 seconds.

In the processing method of the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the bleaching solution and the fixing solution. The reason is that not only the effects of the object of the present invention are better exhibited, but also rapid processing suitability is obtained. Here, the forced liquid agitation means that 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 Japanese Patent Application No. 63-48930 and Japanese Patent Laid-Open No. 1-206343 can be adopted.

Further, in the present invention, the crossover time between the color developing tank and the bleaching tank is 11
Within seconds, preferably within 7 seconds is effective against bleaching fog, which is a different effect from the present invention, and 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 the present invention. Is a preferred embodiment for carrying out.

Next, the stabilizing solution will be described. The stabilizing solution preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constant is defined by LG Sillen / AEMartell, "St.
ability Constants of Metal-ion Complexes ", The Chem
ical Society, London (1964). S.Chaberek ・ AE Martell
It means a constant generally known by "Organic Sequestering Agents", Wiley (1959), etc.

As a chelating agent having a chelate stability constant for ferric ions of 8 or more, Japanese Patent Application No. 2-234776,
Examples thereof include those described in No. 1-324507.

The amount of the above chelating agent used is stable tank liquid 1
0.01 to 50 g per liter is preferable, more preferably
Good results are obtained in the range of 0.05 to 20 g.

Further, as a preferable compound to be added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. The amount of the ammonium compound added is preferably in the range of 0.001 mol to 1.0 mol, and more preferably in the range of 0.002 to 2.0 mol, per liter of the stable tank liquid.

Further, it is preferable that the stable tank liquid contains sulfite.

Further, it is preferable that the stable tank liquid contains a surfactant. As a surfactant, Japanese Patent Application No. 2-2740
Examples of the water-soluble organic siloxane-based compound represented by the general formula [II] described on page 6 of No. 26 specification and the exemplified compounds II-1 to 17 described on pages 67 to 70 of the same specification, and preferably II-1 ,
II-3, II-7, II-13, II-15, II-16, II-17. Further, compounds represented by the general formulas [I] to [II] described in JP-A-62-250449 may be used. Regarding the amount of addition, the same specification or publication can be referred to.

Furthermore, it is preferable that the stable tank liquid contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi,
There is a metal salt of Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr, and it is supplied as an inorganic salt such as halide, hydroxide, sulfate, carbonate, phosphate, acetate, etc. or as a water-soluble chelating agent. it can.
The amount used is 1 x 10 ^-4 per liter of stable tank liquid.
It is preferably in the range of 1 × 10 ^-1 mol, more preferably 4 ×.
It is in the range of 10 ^{−4 to} 2 × 10 ⁻² mol.

The stable tank liquid also contains organic acid salts (hydrochloric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) Agents and the like can be added.

In the process of the present invention, silver may be recovered from the stabilizing solution. Further, the stabilizing solution is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (see JP-A-60-241053, 62-254151, and JP-A-2-132440). ), Etc. Further, it is also preferable to use the deionized water used in the stabilizing solution in advance. That is, the anti-vibration property of the stabilizing solution, the stability of the stabilizing solution, and the image storability can be improved. Any means can be used for the deionization treatment as long as the Ca, Mg ions in the wash water after the treatment are 5 ppm or less. For example, the treatment with an ion exchange resin or a reverse osmosis membrane can be used alone or in combination. preferable. Regarding the ion exchange resin and reverse osmosis membrane, open technical report 87-1
Details are given in No. 984.

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

It is preferable that the stable tank is composed of a plurality of tanks, preferably 2 to 6 tanks, particularly preferably 2 to 3 tanks, and more preferably 2 tanks. It is preferable to use a system in which the solution is supplied to the bath to overflow from the previous bath).

The treatment temperature of the treatment with the stabilizing solution is preferably 15 to 70 ° C, more preferably 20 to 55 ° C.

The pH value of the stabilizing solution is preferably pH 6.0 or more, more preferably 7 for the purpose of improving the image storability.
As described above, the range of 7.5 to 9.0 is particularly preferable.

The processing time of the stabilizing solution is preferably 2 minutes or less,
The time is more preferably 1 minute and 30 seconds or less, and particularly preferably 1 minute or less from the viewpoint of rapid processing.

Next, the colored magenta coupler represented by the general formula [CM-I] contained in the silver halide color photographic light-sensitive material of the present invention will be described.

In the general formula [CM-I], the substituent represented by R ₁ is, for example, an alkyl group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group,
Examples thereof include a hydroxyl group, a halogen atom, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group and a carboxyl group, and these groups may further have a substituent. R ₁ is preferably an alkyl group, an alkoxy group, a hydroxy group or an acylamino group, and most preferably an alkoxy group.

The acylamino group represented by R ₂ is
For example, 2,4-di-t-pentylphenoxyacetamide group, 4
Examples include-(2,4-di-t-pentylphenoxy) butanamide group, examples of the sulfonamide group include 4-dodecyloxyphenylsulfonamide group, and examples of the imide group include octadecenylsuccinimide. Examples of the carbamoyl group include 4- (2,4-di-t-
Pentylphenoxy) butylaminocarbonyl group, examples of the sulfamoyl group include a tetradecanesulfamoyl group, and examples of the alkoxy group include:
Examples thereof include a methoxy group, ethoxy group and octyloxy group, examples of the alkoxycarbonyl group include a tetradecaneoxycarbonyl group, and examples of the alkoxycarbonylamino group include a dodecyloxycarbonylamino group. Preferred as R ₂ is an acylamino group substituted in the p-position with respect to R ₃ .

Examples of the halogen atom represented by R ₃ include chlorine atom, bromine atom and fluorine atom, and examples of the alkoxy group include methoxy group and dodecyloxy group. R ₃ is preferably a chlorine atom. Further, m is preferably 1 or 2, and n
Is 1.

Hereinafter, the above general formula [CM-
Specific examples of the compound represented by the formula [I] are shown below, but the present invention is not limited thereto.

[0126]

[Chemical 8]

[0127]

[Chemical 9]

[0128]

[Chemical 10]

[0129]

[Chemical 11]

[0130]

[Chemical 12]

[0131]

[Chemical 13]

Colored magenta coupler [CM-I]
Can be generally synthesized by a commonly used so-called diazo coupling reaction, for example, by the method described in Japanese Patent Publication No. 56-6540. That is, 1 to 5 of the aniline derivative in water, hydrous alcohol, or hydrous acetone.
Diazotization was carried out at 0 to -10 ° C with 1 mol to 2 mol of concentrated hydrochloric acid and 1 to 1.2 mol of sodium nitrite, and this solution was placed in a pyridine solution of a magenta coupler equimolar to the above aniline derivative prepared separately. , At -5 to -10 ° C, and the diazo coupling is carried out to easily obtain the desired colored coupler.

The colored magenta coupler [CM-I] of the present invention may be used alone or in combination of two or more.

The addition amount of the colored magenta coupler [CM-I] is not limited, but the magenta coupler [M-
1/20 to 1/2 mol of I] is suitable and can be appropriately increased or decreased depending on the types (characteristics) of silver halide, magenta coupler and colored coupler.

In order to incorporate the magenta coupler and the colored magenta coupler [CM-I] into the silver halide emulsion layer, a conventionally known method, for example, a known high-boiling point solvent such as dibutyl phthalate or tricresyl phosphate is used. The magenta coupler and the colored magenta coupler [CM-I] are dissolved in a mixed solution of a low boiling point solvent such as butyl acetate and ethyl acetate, or in a solvent containing only a low boiling point solvent alone or in combination, and then a surfactant is dissolved. It is possible to employ a method in which it is mixed with a gelatin aqueous solution containing, then emulsified and dispersed using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then directly added to the emulsion. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the magenta coupler and the colored magenta coupler [CM-I] may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but the magenta coupler and the colored magenta coupler [CM-I] may be added. CM-I] is dissolved at the same time, dispersed, and added to the emulsion.

The light-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a silver halide emulsion.

The silver halide emulsion of the present invention includes silver chloride, silver bromide, silver iodide or mixed silver halides, such as silver chlorobromide, silver iodobromide, silver chloroiodide, and silver iodobromide. Can be applied. These silver halide emulsions are produced by a usual method, and an ammonia method, a neutral method, an acidic method, a halogen conversion method, a function addition method, a uniform precipitation method, or the like can be applied. The average diameter of the particles is not limited, but 0.01 μm to 5 μm is preferable. Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed using a conventional method. The chemical sensitization includes gold sensitization using a gold complex salt, reduction sensitization using a reducing substance, sulfur sensitization using a compound containing sulfur capable of reacting with silver ions or so-called activated gelatin, and cyclic sensitization. A sensitization method using a salt of a noble metal belonging to Group VIII of the table can be used.

The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. As the method, cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine, and carbocyanine can be used alone or in combination, or can be used in combination with a styryl dye or an aminostilbene compound.

The silver halide emulsion used in the present invention includes stabilizers, antifoggants, surfactants, defoamers, antistatic agents, hardeners, film physical property improvers, brighteners and stain inhibitors. ,
Additives such as an ultraviolet absorber and an anti-irradiation agent can be included. About these various additives
All those described in Research Disclosure Volume 176, No. 17643 (1978) can be used.

The support of the color photographic light-sensitive material of the present invention comprises
It can be appropriately selected according to the purpose. For example, cellulose acetate film, polyethylene terephthalate film, polystyrene film, polycarbonate film, or laminates of these, paper, baryta paper, α-
Paper coated with olefin polymer, synthetic paper, glass,
There are metals, etc.

In the color photographic light-sensitive material described above, it is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, and hydroxy. Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. It is possible to mix and use various types of synthetic hydrophilic polymer substances.

[0144]

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

Example 1 [Preparation of Treated Tablet for Color Negative Film] 1) Color development replenishing tablet operation for color negative (1) Developing agent CD-4 [4-amino-3-methyl-N-ethyl-β-
(Hydroxy) ethylaniline sulfate] 130 g is pulverized in an air jet fine pulverizer until the average particle size becomes 10 μm. After granulating this fine powder by spraying 5.0 ml of water at room temperature for about 7 minutes in a commercial fluidized bed spray granulator,
The granulate is dried at 63 ° C for 8 minutes. Then granulate in vacuum
The granules are dried at 40 ° C. for 2 hours to almost completely remove water.

Operation (2) 64 g of hydroxylamine sulfate are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 2.6 ml, and after granulation, 60 ℃
Dry for 7 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (3) 1-hydroxyethane-1,1-diphosphonate disodium salt 60
g, sodium sulfite 80 g, potassium carbonate 700 g, sodium hydrogen carbonate 60 g, sodium bromide 8 g, diethylenetriamine pentaacetic acid 60 g and sodium lauryl sulfate 50 g
Is pulverized in the same manner as in (1), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (1), the amount of water sprayed is set to 200 ml and granulation is performed. After granulation, the granulate is dried at 70 ° C. for 15 minutes and then the granulate is dried in vacuum at 40 ° C. for 2 hours to remove almost completely the water of the granulate.

Operation (4) The granules prepared in the above operations (1) to (3) were subjected to 40 ° C. at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room conditioned to below% RH. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 5.8 g, to prepare 160 color developing and developing tablets for color negative.

2) Bleaching Replenishing Tablet for Color Negative Operation (5) 1,3-Propanediaminetetraacetic acid ferric ammonium monohydrate
175 g, 60 g of succinic acid, 73 g of maleic acid and 2 g of 1,3-propanediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 5.0 ml, and after granulation, it is dried at 60 ° C. for 7 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product.

Operation (6) Using 80 g of potassium nitrate, 200 g of ammonium bromide, 60 g of potassium carbonate and 30 g of sodium lauryl sulfate, operation (1)
Grind and granulate in the same manner as in. The amount of water sprayed is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Then granulate in vacuum
The granulated product is dried at 2 ° C. for 2 hours to almost completely remove water.

Operation (7) The granules prepared in the above operations (5) and (6) were subjected to 40 ° C. at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room conditioned to below% RH. Next, the mixture was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho, so that the filling amount per tablet was 6.5 g, and 80 bleaching tablets for color negative bleaching were prepared.

3) Fixing replenishing tablet operation for color negative (8) Ammonium thiosulfate 2500 g, sodium sulfite 150
g, potassium carbonate 150 g, ethylenediamine tetraacetic acid disodium salt 20 g and sodium benzoate 60 g are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 30 ml, and after granulation, it is dried at 60 ° C for 60 minutes. Next, the granulated product is dried in vacuum at 40 ° C. for 8 hours to almost completely remove the water content of the granulated product.

Operation (9) The granulated product prepared in the above operation (8) is uniformly mixed for 10 minutes using a mixer in a room where the humidity is controlled to 40% RH or less at 25 ° C. Next, mix the mixture with Kikusui Seisakusho Tough Press Collect 15
Filling amount per tablet is 9. with a tablet machine modified from 27HU.
The tablets were compressed and compressed to 3 g to prepare 200 fixing replenishing tablets for color negative.

4) Tablet for stable replenishment for color negative (10) m-Hydroxybenzaldehyde 200 g, Emulgen 985;
10 g, 45 g of potassium carbonate and 20 g of sodium benzoate are ground and granulated in the same manner as in the operation (1). The amount of water sprayed is 3.0 m
After granulation, the granulated product is dried in vacuum at 30 ° C. for 8 hours to almost completely remove the water content of the granulated product.

Operation (11) The granulated product prepared in the above operation (10) is uniformly mixed for 10 minutes using a mixer in a room where the humidity is adjusted to 40% RH or less at 25 ° C. Next, mix the mixture with Kikusui Seisakusho Tough Press Collect 15
The tablet filling machine modified from 27HU reduces the filling amount per tablet to 0.
The tablets were compressed and compressed to 2 g to prepare 1060 fixing fixing tablets for color negative.

Next, on the triacetyl cellulose film support, each layer having the following composition was sequentially formed from the support side to prepare a color photographic light-sensitive material sample 1.

In this embodiment, 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. Further, the sensitizing dye is shown by the number of moles per mole of silver.

First layer; antihalation layer (HC) Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.20 High boiling point solvent (Oil-) 2) 0.20 gelatin 1.6 second layer; intermediate layer (IL-1) gelatin 1.3 third layer; low-sensitivity red-sensitive emulsion layer (RL) silver iodobromide emulsion (Em-1) 0.4 silver iodobromide emulsion (Em- 2) 0.3 sensitizing dye (S-1) 3.2 × 10 ^-4 sensitizing dye (S-2) 3.2 × 10 ^-4 sensitizing dye (S-3) 0.2 × 10 ^-4 cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling point solvent (Oil-1) 0.55 Additive (SC-1) 0.003 Gelatin 1.0 4th layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em- ) 0.9 Sensitizing dye (S-1) 1.7 × 10 -4 Sensitizing dye (S-2) 1.6 × 10 -4 Sensitizing dye (S-3) 0.1 × 10 -4 Cyan coupler (C-2) 0.23 Colored Cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling point solvent (Oil-1) 0.25 Additive (SC-1) 0.003 Gelatin 0.1 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 Sixth Layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Sensitizing dye (S-4) 6.7 × 10 ^-4 sensitization Dye (S-5) 0.8 × 10 ^-4 Magenta coupler (M-1) 0.17 Magenta coupler (M-2) 0.43 Colored magenta coupler (CM-A) 0.10 DIR compound (D-3) 0.02 High boiling solvent (Oil- 2) 0.70 additive (SC-1) 0.003 gelatin 1.0 seventh layer; high-sensitivity green-sensitive emulsion layer (GH) silver iodobromide emulsion (Em-3) 0.9 Sensitive dye (S-6) 1.1 × 10 -4 Sensitizing dye (S-7) 2.0 × 10 -4 Sensitizing dye (S-8) 0.3 × 10 -4 Magenta coupler (M-1) 0.03 Magenta coupler (M -2) 0.13 Colored magenta coupler (CM-A) 0.04 DIR compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 Eighth layer; (IL-3) Gelatin 1.0 9th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling point solvent (Oil-2) 0.15 Gelatin 1.0 10th layer: low-sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (Em-1) 0.25 silver iodobromide emulsion (Em-2) 0.25 sensitizing dye (S-9) 5.8 × 10 ^-4 yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-1) 0. 03 DIR compound (D-2) 0.006 High boiling point solvent (Oil-2) 0.18 Additive (SC-1) 0.004 Gelatin 1.3 11th layer; High sensitivity blue sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4 ) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 Sensitizing dye (S-11) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling solvent (Oil- 2) 0.05 Additive (SC-1) 0.002 Gelatin 1.0 12th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (Em-5) 0.3 UV absorber (UV-1) 0.07 UV absorber ( UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 0.8 13th layer; 2nd protective layer ( PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (flat Particle size 3 μm) 0.02 Sliding agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (SU-2) 0.02 Gelatin 0.5 In addition to the above composition, each layer contains coating aid SU- 4, dispersion aid SU-3, hardeners H-1, H-2, stabilizer ST-
1. Preservative DI-1, antifoggant AF-1, AF-
2. Dyes AI-1 and AI-2 were added appropriately.

The emulsions used in the above samples are as follows. Both are internal high iodine type monodisperse emulsions.

Em-1: Average silver iodide content 7.5 mol%
Average grain size 0.55 μm Grain shape Octahedron Em-2: Average silver iodide content 2.5 mol% Average grain size
0.36 μm grain shape octahedron Em-3: average silver iodide content 8.0 mol% average grain size
0.84 μm grain shape octahedron Em-4: average silver iodide content 8.5 mol% average grain size
1.02 μm grain shape octahedron Em-5: average silver iodide content 2.0 mol% average grain size
0.08μm particle shape octahedron

[0161]

[Chemical 14]

[0162]

[Chemical 15]

[0163]

[Chemical 16]

[0164]

[Chemical 17]

[0165]

[Chemical 18]

[0166]

[Chemical 19]

[0167]

[Chemical 20]

[0168]

[Chemical 21]

Samples 2 to 20 were prepared by substituting the colored magenta coupler CM-A in the sixth and seventh layers of Sample 1 with the same amount of the colored magenta coupler as shown in Table 1.

Samples 1 to 20 thus obtained are
After cutting to a width of 35 mm, a wedge exposure is given by a conventional method,
The fog (Fog ₁ ) of the green photosensitive emulsion layer before the running treatment of each sample was determined by the following treatment steps.

Next, each sample cut into a width of 35 mm was put in a camera, photographed with proper exposure, and continuously processed until the cumulative replenishment amount of hot water to the color developing tank reached 20 l by the following processing steps. After that, each sample subjected to wedge exposure was processed in the same manner as above, and the fog (Fog ₂ ) of the green photosensitive emulsion layer of each sample after the running process was determined.

The fog is the green light density when each unexposed sample is processed by the following development process except color development, and the green light density of each sample after the wedge exposure and the following processes. It was calculated from the difference from the lowest concentration. The processing conditions and processing solutions of the examples will be described below. [Development] Konica Color Negative Film Processor C
The L-KP-50QA was provided with a tablet supply function, a liquid level detection function, a hot water supply function and the like by modification, and the following treatments were performed. The standard processing conditions for the automatic processing machine are shown below.

[0173] The stabilizer is replenished in the third tank, and the overflow solution is successively flown into the first tank and the second tank.

The processing liquid for the automatic processing machine was prepared by the following method.

Color development tank liquid (21.0 liters) 15 liters of warm water at 35 ° C. was placed in the developing machine color development tank, and 399 color development replenishing tablets for color negative film prepared in the same manner as in Example 1 were added and dissolved. did. Next, a starter of the following formulation, which was separately tableted as a starter component, was used.
After pouring and dissolving, warm water was added up to the tank mark to complete the tank solution.

Color Development Starter for Color Negative Sodium Bromide 0.8 g Sodium Iodide 2.0 mg Sodium Hydrogencarbonate 3.0 g Potassium Carbonate 0.5 g Bleaching Solution (5.0 l) 3.0 l of 35 ° C. warm water was placed in a bleaching tank of the developing machine, 1
350 bleaching replenishing tablets for color negative film prepared in the same manner as in (3) were added and dissolved. Next, tablet it separately as a starter component and add 10 starters of the following formulation,
After dissolution, warm water was added to the tank line to complete the tank solution.

Bleaching Starter for Color Negative Potassium Bromide 10.0 g Sodium Bicarbonate 1.5 g Potassium Carbonate 3.5 g Fixer (4.5 liter for the first tank, 4.5 liter for the second tank) 35 3 ° C warm water each.
Then, 112 tablets of fixing replenisher for color negative film prepared in the same manner as in Example 1 were charged and dissolved. Next, warm water was added to the tank line to complete the tank solution.

Stabilizer (3.2 liters for each of the first to third tanks) Prepared in the same manner as in Example 1 by adding 3.0 liters of hot water at 35 ° C. to the first, second, and third tanks of the developing machine fixing tank. 40 tablets for stable replenisher for color negative film were added and dissolved. Next, hot water was added up to the tank mark to complete the tank solution.

Next, during the humidity control of the automatic developing machine, 20 tablets of the respective supplemental tablets prepared in Example 1 were set in the supplementary tablet supplying device provided to the automatic developing machine. This replenishing tablet is fed one by one when two 135 size 24 film films are processed. At the same time, replenishing hot water from the hot water supply device is 40 ml in the color developing tank, 10 ml in the bleaching tank and 40 ml in the fixing tank. , 80 ml was supplied to the stabilizing tank.

The results are shown in Table 1.

[0181]

[Table 1]

[0182]

According to the method of processing a silver halide color photographic light-sensitive material of the present invention, an image with less fog can be obtained when a tableting silver halide photographic light-sensitive material processing agent is used.

Claims (3)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer containing a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and at least one of the photographic constituent layers is at least a colored magenta coupler represented by the following general formula [CM-I]. A silver halide color photographic light-sensitive material, characterized in that a silver halide color photographic light-sensitive material containing one is processed with a processing solution prepared using a tableting silver halide photographic light-sensitive material processing agent. Processing method. [Chemical 1] [Wherein R ₁ represents a substituent, R ₂ represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group or an alkoxycarbonylamino group, and R ₃ represents a halogen atom. Alternatively, it represents an alkoxy group. m is 0-5, n is 0
Represents an integer of 4; ] 2. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein the tableted processing agent for silver halide photographic light-sensitive material contains at least one water-soluble lubricant. Method. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the water-soluble lubricant is at least one selected from alkali metal lauryl sulfate, alkali metal benzoate and polyethylene glycol. Material processing method.