JPH06130593A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the method for processing the silver halide color photographic sensitive material small in fog and yellow stains in the storage of an image at the time of processing it with a processing solution prepared by using a tabletted material with a processing solution prepared by using a tabletted processing agent. CONSTITUTION:The silver halide color photographic sensitive material has on a support photographic constituent layers including blue-, green-, and red- silver halide emulsion layers and it is characterized by being processed with the processing solution prepared by using the tabletted processing agent.

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]

BACKGROUND OF THE INVENTION Color light-sensitive materials for photographing are usually subjected to color development, bleaching, fixing, washing and / or stabilizing steps after exposure, and color paper light-sensitive materials are subjected to color development after exposure.
Processing is carried out by bleach-fixing (bleaching, fixing), washing and / or stabilizing steps, and the black-and-white light-sensitive material is usually processed by developing, fixing and washing steps 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, when a silver halide color photographic light-sensitive material is processed by using a tableting processing agent, there is a drawback that fog increases and yellow stain increases in image storage. Became.

[0009]

OBJECT OF THE INVENTION The object of the present invention is to prevent fog and yellow stain in image storage when processing is carried out using a processing solution prepared using a tableting processing agent for silver halide photographic light-sensitive materials. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material having less amount of waste.

[0010]

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

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 contains gelatin cross-linked with at least one vinyl sulfone hardener. A method of processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material with a processing liquid prepared using a tableting silver halide photographic light-sensitive material processing agent.

The method of processing a silver halide color photographic light-sensitive material as described above, wherein the tableted processing agent for silver halide photographic light-sensitive material contains at least one water-soluble lubricant.

The method for processing a silver halide color photographic light-sensitive material as described 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 -C
ON (C _m H _{2m + 1} ) ₂ , (m and n each represent an integer of 0 or more), —COOH, —SO ₃ H and the like can be mentioned as preferable ones.

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 are carboxylic acid groups, phosphoric acid groups,
It may have 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 be bonded to form a ring, for example, piperidine, pyridine, triazine and morpholine. Heterocycles such as

[0048]

[Chemical 1]

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 3,287,124 and the like, particularly preferred specific exemplary compounds include Japanese Patent Application No. 2-203169, No. 36 to
(I-1) to (I-39) described on page 38 and JP-A-3-33845.
(1) to (53) described in pages 3 to 6 of the specification and JP-A-3-
(1) to (52) described on pages 5 to 7 of the 63646 specification.

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, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

It is preferable that the color developer contains substantially no benzyl alcohol. Substantially no more than 2.0 ml per liter of color developing tank solution, more preferably no content 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 2]

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 3]

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 4]

[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 represents 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.
It is not limited to these.

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 ₂ -COOH) ₂ IV-3 (HOOC-CH ₂ ) ₂ N-CH ₂ -C (CH ₃ ) _2- CH ₂ -N (CH ₂ -COOH) ₂ (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 addition to the above, the bleaching solution or the bleach-fixing solution may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

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 enhance 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 a pH buffering agent consisting of various salts, either alone or in combination of two or more kinds. 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 bleach-fixing solution can be prepared by the following general formula [F] described in JP-A 64-295258, page 56.
The compound represented by A] and this exemplified compound may be added.

[0098]

[Chemical 5]

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 to 10 of the specification of WO91 / 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 of 8 or more with respect to ferric ion, 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 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 (phosphoric acid salts, boric acid salts, hydrochloric acid, sulfuric acid salts, etc.), and anti-biological agents. 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 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 vinyl sulfone type hardener according to the present invention will be described.

The vinyl sulfone type hardener used in the present invention is, for example, an aromatic compound as described in German Patent No. 1,100,942 and US Pat. No. 3,490,911,
Alkyl compounds bound by a hetero atom as described in JP-B-44-29622, JP-A-47-25373, JP-A-47-24259 and the like, sulfonamides as described in JP-B-47-8736 and the like, Ester compounds, 1,3,5-tris [β- (vinylsulfonyl) -propionyl] -hexahydro-s-triazine as described in JP-A-49-24435 or JP-B-50-35807, It includes an alkyl compound as described in JP-A-51-44164 and the like, a compound as described in JP-A-59-18944 and the like.

The vinyl sulfone type hardener which is preferably used in the present invention is represented by the following general formula [HI].

[0125]

[Chemical 6]

In the above general formula [HI], L is a w-valent linking group, which may be substituted, and X is -CH = CH.
₂ or —CH ₂ CH ₂ Y, Y is a group which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (for example, a halogen atom, a sulfonyloxy group, a monosulfate sulfate). Ester).

W represents an integer of 2 to 10.

The w-valent linking group L is, for example, an alkylene group,
An arylene group or these groups, -O-, -N (R ¹ )-,-
CO -, - SO -, - SO 2 -, - SO 3 -, - SO 2 N (R 1) -, - CO
M-valency formed by combining one or more bonds represented by O-, -CON (R ¹ )-, -N (R ¹ ) CON (R ¹ )-, -N (R ¹ ) CO _2- It is the basis of R ¹ represents a hydrogen atom, or an alkyl group having 1 to 15 carbon atoms or an aralkyl group. Also, -N (R ¹ )-, -SO ₂ N (R ¹ )-, -CON (R ¹ )-,
When two or more —N (R ¹ ) CO ₂ — are contained, those R ^{1 s} may combine to form a ring. Further, L may have a substituent, and as the substituent, a hydroxyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group,
An aryl group etc. are mentioned as an example. Further, the substituent may be further substituted with one or more groups represented by X ³ —SO ₂ —. X ³ has the same meaning as X described above.

The following are typical examples of L. However, a to v in the examples may be integers from 1 to 6, and only d may be 0. Of these, d, k, l
And p are preferably 1 to 3, and a-v other than d, k, l and p is preferably 1 or 2. R ¹ is preferably a hydrogen atom or an alkyl group having a monovalent to hexavalent carbon atom, and particularly preferably a hydrogen atom, a methyl group and an ethyl group.

[0130]

[Chemical 7]

Specific examples of X include the following.

[0132]

[Chemical 8]

Of these, -CH = CH ₂ , -CH ₂ CH ₂ C
l, -CH ₂ CH ₂ Br, -CH ₂ CH ₂ OSO ₂ CH ₃ and -CH ₂ CH ₂ OSO ₃ Na
Is preferred.

Typical examples of the vinyl sulfone type hardener according to the present invention are shown below.

[0135]

[Chemical 9]

[0136]

[Chemical 10]

[0137]

[Chemical 11]

[0138]

[Chemical 12]

[0139]

[Chemical 13]

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

The layer in which these hardeners are added to the photographic layer is not particularly limited, and the object of the present invention can be achieved by adding them to, for example, one uppermost layer, one lowermost layer or all layers. You can

Since the above-mentioned hardener is highly diffusible in the photographic constituent layers, when all the photographic constituent layers are simultaneously coated,
Before being hardened even if it is added to any of the constituent layers that are simultaneously coated, or even when it is simultaneously coated while exhibiting the hardenability, almost all layers of the photographic constituent layer are eventually spread to all layers. It is possible to harden the film almost uniformly.

The photosensitive 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, film physical property improvers, brighteners, stain inhibitors, and ultraviolet absorbers. An additive such as an anti-irradiation agent can be included. Researc for these various additives
h 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 above color photographic light-sensitive material, 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.

[0150]

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

Example 1 [Preparation of Color Paper Treated Tablets] 1) Color development replenishment tablet operation for color paper (A) Developing agent CD-3 [4-amino-3-methyl-N-ethyl-N-]
120 g of [β- (methanesulfonamido) ethyl] aniline sulphate] is pulverized in an air jet pulverizer until the average particle size becomes 10 μm. This fine powder is granulated by spraying 4.5 ml of water in a commercially available fluidized bed spray granulator for about 5 minutes at room temperature, and then the granulated product is dried at 60 ° C. for 8 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 (B) Disulfoneethylhydroxylamine disodium salt 12
0 g is crushed and granulated in the same manner as in the operation (A). The amount of water spray is
After granulating to 3.0 ml, it is dried at 50 ° C for 10 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 (C) Chinopearl SFP (manufactured by Ciba Geigy) 30.0 g, sodium sulfite 3.7 g, potassium carbonate 350 g, potassium bromide 0.3
g, 25 g of diethylenetriamine pentaacetic acid, 300 g of sodium p-toluenesulfonate and 20 g of potassium hydroxide were pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), 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 (D) The granules prepared in the above operations (A) to (C) are 40% at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Next, add 50 g of sodium lauryl sulfate,
Mix for an additional 5 minutes. 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 7.85 g, to prepare 150 color development replenishing tablets for color paper.

2) Bleach-fixing replenishing tablet for color paper Operation (E) Ethylenediaminetetraacetic acid ferric ammonium monohydrate 550
20 g of ethylenediaminetetraacetic acid and 200 g of maleic acid are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 25.0 ml, and after granulation, it is dried at 60 ° C for 15 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 (F) Ammonium thiosulfate (725 g), sodium sulfite (300 g), potassium bromide (170 g) and p-toluenesulfinic acid (20 g) are pulverized and granulated in the same manner as in operation (A). The amount of water sprayed is 15.0 ml, and after granulation, it is dried at 60 ° C for 10 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 (G) The granules prepared in the above operations (E) and (F) are 40% at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Then add 50 g of sodium benzoate and mix for an additional 5 minutes. 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 39.7 g, and 100 bleach-fixing supplement tablets for color paper were prepared.

3) Stable replenishing tablet for color paper (H) Sodium carbonate monohydrate 10 g, 1-hydroxyethane-1,1-
200 g of disodium diphosphonate is ground and granulated in the same manner as in the operation (A). The amount of water sprayed is 1.0 ml, and after granulation, 70 ℃
Dry for 3 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 (I) Tinopearl SFP 150 g, sodium sulfite 300 g, zinc sulfate heptahydrate 20 g, ethylenediamine tetraacetic acid disodium 150
g, ammonium sulfate 200 g, and o-phenylphenol 10 g are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 10.0
After granulating, it is dried at 65 ° C for 5 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 (J) The granules prepared in the above operations (H) and (I) are 40% at 25 ° C.
Mix evenly for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Then 30 g of sodium benzoate is added and mixed for another 5 minutes. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho, with the filling amount per tablet being 2.6 g, to prepare 400 stable supplementary tablets for color paper.

[Preparation of Photosensitive Material] Each layer having the constitution shown in Tables 1 and 2 below was oxidized on a paper support having polyethylene laminated on one side and polyethylene containing titanium oxide on the other side. A multi-layer silver halide color photographic light-sensitive material sample 1 was prepared by coating on the side of the polyethylene layer containing titanium. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (YA) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.
To 67 g, 0.67 g of the additive (HQ-1) and 6.67 g of the high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution contained 7 ml of a 20% aqueous solution of the surfactant (SU-1) 10 % Gelatin aqueous solution 220 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, 0.06 g / m ² of (HA) was added to each of the second, fourth and seventh layers as a hardening agent. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

[0164]

[Table 1]

[0165]

[Table 2]

[0166]

[Chemical 14]

[0167]

[Chemical 15]

[0168]

[Chemical 16]

[0169]

[Chemical 17]

(Preparation of silver halide emulsion) Three kinds of silver halide emulsions shown in Table 3 were prepared by a neutral method and a simultaneous mixing method.

[0171]

[Table 3]

To each silver halide emulsion, after the chemical sensitization, STB-1 shown below as an emulsion stabilizer was added in an amount of 5 × 10 ⁻³ mol per mol of silver halide.

[0173]

[Chemical 18]

Next, the hardener (H
-A) was replaced with the same amount of the hardener shown in Table 4 to prepare Samples 2 to 20.

Samples 1 to 20 thus obtained
Wedge exposure is carried out by a conventional method, and processing is performed by the following processing steps, and the fog (F
og) was calculated.

[0176] Further, the above-mentioned treated samples were treated at 55 ° C and humidity of 80%.
After leaving it for 10 days under the conditions described above, the density (yellow stain) of the unexposed area was measured with blue light.

The results are shown in Table 4.

[Development Processing] Konica Color Paper Type Q
A processor CL-PP-718 was provided with a tablet supply function, a liquid level detection function, a hot water supply function, etc. by modification, and the following processing was performed. The standard processing conditions of the automatic processing machine are shown below.

Processing step Temperature Time Color development 38 ± 0.3 ° C. 25 seconds Bleach-fixing 35 ± 1.0 ° C. 25 seconds Stability −1 33 ± 3.0 ° C. 20 seconds Stable-2 33 ± 3.0 ° C. 20 seconds Stable-3 33 ± 3.0 ° C. 20 seconds Drying 72 ± 5.0 ℃ 40 seconds Stabilizer is replenished in the third tank, and the overflow system is a cascade method in which two tanks and one tank sequentially flow.

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

Color developing tank liquid (23.0 l) 18 l of hot water at 35 ° C. was placed in the developing machine color developing tank, and 314 color developing replenishing tablets for color paper prepared in the same manner as in Example were charged and dissolved. . Next, 23 starters of the following prescription, which were separately tabletted as starter ingredients, were added,
After dissolution, warm water was added up to the tank mark to complete the tank solution.

Color development starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g Bleach-fixing solution (23.0 l) Put 15 l of 35 ° C. hot water in the automatic bleach-fixing tank, and perform as in the example. 292 bleach-fixing replenishing tablets for color paper prepared in the above were added and dissolved. After dissolution, warm water was added to the tank line to complete the tank solution.

Stabilizer (15 liters for each of the first to third tanks) 12 l of warm water at 35 ° C. was added to each of the first, second, and third tanks for stabilizing the automatic developing machine, and the same procedure as in the example was performed. 60 stable replenishment tablets for color paper were added and dissolved. Next, warm water was added to the tank line to complete the tank solution.

Next, during the temperature control of the automatic developing machine, the respective supplemental tablets prepared in the examples were applied to the supplemental tablet supplying device provided to the automatic developing machine.
I set 20 pieces. This refill tablet has a color paper of 1 m ²
When processed, they are added one by one, and at the same time, supplemented hot water from the hot water supply device is 80 ml in the color developing tank and 200 m in the bleach-fixing tank.
l, 250 ml was set in the stabilizing tank.

[0185]

[Table 4]

As is clear from the table, when the sample 1 other than the present invention is treated with the tableting treatment agent, the fog is large and the yellow stain in image preservation is large.

On the other hand, in Samples 2 to 20 using the heterocyclic antifoggant of the present invention, there is little fog even when treated with the tableting treatment agent, and the yellow stain in image preservation is small. Few.

[0188]

According to the present invention, when the processing is carried out using the tableting silver halide photographic light-sensitive material processing agent, fog and silver halide color photographic light-sensitivity with little yellow stain in image storage are reduced. A method of treating material can be provided.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing an example of an automatic developing machine according to the present invention.

FIG. 2 is a schematic explanatory diagram of an example showing a state of sending out and supplying a solid processing agent.

[Explanation of symbols]

 1 color developing tank 2 bleach-fixing tank 3 water washing tank 4 stabilizing tank 5 drying section 7 photosensitive material area detection sensor 8 solid processing agent replenishing device 9 liquid level detection sensor 10 replenishing water replenishing device 11 control section 12 solenoid valve 13 photosensitive material insertion section 14 Washing hot water 15 Replenishment water supply pipe 16 Main treatment tank 17 Treatment liquid 18 Circulation pump 19 Temperature control heater 20 Sub tank 20A Guide plate 20B Ceiling cover 21 Filtration device 24 Solid treatment agent 24A Solid treatment agent on top 27 Communication pipe 28 Treatment rack 29 Overflow port 39 Filtration filter 91 Supply tray body 92 Piston slide 94, 99 Plunger 94A, 99A Rack 95, 97 Stepping motor 96, 98 Pinion

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 contains gelatin cross-linked with at least one vinyl sulfone hardener. A method of processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material with a processing liquid prepared using a tableting silver halide photographic light-sensitive material processing agent. 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.