JPH06102628A - Solid processing agent for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the solid processing agent for the silver halide photographic sensitive material not only superior in luster but also high in strength, not causing scratches on the film in processing the photosensitive material and any stain on rollers in an automatic developing machine and any precipitate in a fixing bath and a bleach-fixing bath. CONSTITUTION:This solid processing agent for the photosensitive material is prepared by tabletting the processing agent containing a water-soluble lustering agent, preferably, such as boric acid, DL-leucine, alkali metal salts of fatty acid, those of lauryl sulfate, and those of benzoic acid, adipic acid, fumaric acid, sodium sulfate, and polyethylene glycol, especially, alkali metal salts of lauryl sulfate and benzoic acid and polyethylene glycol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid processing agent for silver halide photographic light-sensitive materials, and more specifically, it provides a processing agent which is excellent not only in lubricity but also in high strength. The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material, which is not scratched and does not stain the roller portion of an automatic processor.

[0002]

BACKGROUND OF THE INVENTION Color light-sensitive materials for photographing are usually subjected to color development, bleaching, fixing, washing with water and / or stabilization after exposure, and color paper light-sensitive materials are subjected to color development after exposure.
It is processed 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 to further reduce the space.

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.

Conventionally, generally, when continuously molding tablets,
Lubricants are used to prevent defective molding due to friction between powder particles and between powder and the formulation machine. Various lubricants are known as such lubricants, and among them, magnesium stearate is widely used because of its extremely excellent lubricant effect.

However, in the case of producing a tabletted photographic processing agent by tableting using magnesium stearate as a lubricant, while the lubricity is very excellent, the strength of the obtained tablet is It has the drawback of being low.

Further, when a silver halide photographic light-sensitive material is processed using a processing solution obtained from a photographic processing agent tableted with magnesium stearate as a lubricant, scratches may occur on the light-sensitive material, or It has been found that there is a problem in that the roller portion of the automatic processor may be soiled or a precipitate may be generated in the fixing tank or the bleach-fixing tank.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to obtain a processing agent which is not only excellent in lubricity but also has high strength. Further, in processing a light-sensitive material, a film is not scratched, and further, an automatic processor is used. It is an object of the present invention to provide a solid processing agent for silver halide photographic light-sensitive materials, which does not cause contamination of the roller portion and does not cause precipitation in the fixing tank or the bleach-fixing tank.

[0012]

A solid processing agent for a silver halide photographic light-sensitive material (hereinafter referred to as a photographic processing agent if necessary) which achieves the above object is a processing agent containing at least one water-soluble lubricant. Is obtained by tableting.

In the solid processing agent for silver halide photographic light-sensitive material of the present invention, the water-soluble lubricant is boric acid, DL-leucine, fatty acid alkali metal salt, lauryl sulfate alkali metal salt, benzoic acid alkali metal salt. It is preferably at least one selected from adipic acid, fumaric acid, sodium sulfate, and polyethylene glycol, and more preferably the water-soluble lubricant is selected from alkali metal lauryl sulfate, alkali metal benzoate, and polyethylene glycol. Is at least one kind.

The water-soluble lubricant used in the present invention can be applied to all tableting photographic processing agents. For example, color developing agents, bleaching agents, fixing agents, stabilizers used in the processing of color photosensitive materials for photographing, and color developing agents, bleach-fixing agents (bleaching agents, fixing agents), stabilizers used in color paper photosensitive materials. Further, it can be applied to developers and fixing agents used for black and white light-sensitive materials, and various processing agents used for processing reversal type light-sensitive materials (negative or paper).

In the present invention, the content of the water-soluble lubricant is
0.01 to 10 for one processed tablet for photographic light-sensitive material
It is preferably in the range of wt%, and more preferably in the range of 0.1 to 5 wt%.

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-51-61
No. 837, No. 54-155038, No. 52-8802.
The method described in the specification of No. 5, British Patent No. 1213808 can also be adopted. A water-soluble lubricant is contained in such tableting.

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, 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 are used as the water-soluble lubricant. It is preferable to use at least one selected from the above, but in order to effectively achieve the object of the present invention, at least one selected from lauryl sulfate alkali metal salt, benzoic acid alkali metal salt and polyethylene glycol is used. .

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. As the water-soluble binder, polyvinyl alcohol type, methyl cellulose type, polyethylene oxide type, starch type, polyvinyl pyrrolidone type, hydroxypropyl cellulose type,
Examples thereof include 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 water splashes or damage from accidental contact with water by wet hands,
The photographic processing agent is preferably packaged in a moisture-proof packaging material.

The moisture-proof packaging material has a film thickness of 10 to 150.
A film having a thickness of μm is preferable, and a moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene, or polypropylene, kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, or polyvinyl chloride, which can have a moisture resistance effect with polyethylene.
Polyvinylidene chloride, polyamide, polycarbonate,
At least one selected from acrylonitrile-based and metal foils such as aluminum and metallized polymer films is preferable, and a composite material using these may be 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,
The following are listed.

Examples of natural polymers such as polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and derivatives thereof include microbial-produced polymers such as 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. Examples of natural polymers with good biodegradability that are used in blending biodegradable natural polymers into plastics include starch and cellulose, which give shape-disintegrating properties to 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 Material", July 1990, pp. 23-34, etc. can be used. In addition, Biopol (manufactured by ICI), Eco (Union Carbide)
Company), Ecolite (Eco light company), E
Commercially available degradable plastics such as costar (Eco Star) (manufactured by St. Lawrence Starch) and Knuckle P (manufactured by Nippon Unicar) 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 solid 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, and when a predetermined unit is reached. A predetermined amount of the replenishing treatment agent is replenished directly to the treatment tank portion of the automatic developing machine when it is solidified, or one or several pieces thereof.

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 solid photographic processing agent, a preferable result can be obtained by directly replenishing it to the processing tank section of the developing machine, for example, the processing solution tank, and the processing solution circulation system or the temperature control tank and the processing solution filtration filter section. Is obtained.

When the solidified photographic processing agent is used, it is possible to freely change the size and shape of the solid photographic processing agent according to the replenishing unit. Each unit receives a signal from the area detector of the photosensitive material which is processed in a predetermined amount through the replenishing mechanism from the upper part of the liquid tank, processing liquid circulation system, temperature control tank, processing liquid filtration filter section, etc. Is preferably replenished.

Furthermore, the solid photographic processing agent replenishing section is devised so that the processing tank section of the developing machine and the temperature of the outside air and the scattered processing solution due to the photosensitive material to be processed do not come into contact with the solid photographic processing agent before replenishment. It is more preferable that

The photographic solid 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 developer,
First developer for reversal film, infectious developer for squirrel,
Examples thereof include, but are not limited to, color developing solutions for color, bleaching solutions, fixing solutions, bleach-fixing solutions, stop solutions, hardening solutions, stabilizing solutions, fog solutions and toning solutions.

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

The processing solution in which the solid photographic processing agent of the present invention is dissolved and the processing method using the processing solution 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 → Bleaching-fixing-fixing-stability The processing liquid used in the above processing step will be described below. In the following description, the treatment liquid obtained by dissolving the solid treatment agent is referred to as a tank liquid or simply a treatment 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 small.

The p-phenylenediamine-based compound having a hydrophilic group is free from contamination of the light-sensitive material, as compared with the p-phenylenediamine-based compound having no hydrophilic group such as N, N-diethyl-p-phenylenediamine. As for the skin, it has the advantage that the skin is less likely to get rash.

Examples of the hydrophilic group include those having at least one amino group on the p-phenylenediamine compound or on the benzene ring. Specific hydrophilic groups include-(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}

[0042]

[Chemical 1] (M and n each represents an integer of 0 or more.), -COOH, be mentioned as -SO ₃ H and the like are preferable.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169.
Nos. 26 to 31 (C-1) to (C-1)
6), (1) to (8) described in JP-A 61-289350, pages 29 to 31, and JP-A-3-24654.
Nos. 3 to 5 to 9 (1) to (62) are mentioned, and particularly preferred are the exemplified compounds (C-1) and (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.

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, and more preferably 1.0 × 10 ^{−2 to} 1.0 × 10, per liter of the color developing solution.
⁻¹ mol, and more preferably 1.5 × 10 ⁻² to
It is 1.0 × 10 ⁻¹ mol.

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

[0047]

[Chemical 2] In the general formula [I], R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an aryl group,

[0048]

[Chemical 3] However, 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,
You may have 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.

[0050]

[Chemical 4] 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, It represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an 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

[0051]

[Chemical 5] Represents a divalent group selected from, and n is 0 or 1. Particularly when n = 0, 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 shown in US Pat. No. 3,287,125.
Nos. 3,329,034 and 3,287,124, etc., but particularly preferable specific exemplary compounds include (I-1) to (I) described on pages 36 to 38 of Japanese Patent Application No. 2-203169. -39) and JP-A-3-338.
(1) to (53) described on page 3 to 6 of the specification No. 45 and (1) to (53) on page 5 to 7 of the specification of JP-A-3-63646.
(52) is mentioned.

Next, specific examples of the compound represented by the above general formula [II] are described in Japanese Patent Application No. 2-203169, Nos. 40 to 40.
(B-1) to (B-33) described on page 43 and JP-A-3-
(1) to (56) described on pages 4 to 6 of No. 33846.
Is mentioned.

The compounds represented by the general formula [I] or the general formula [II] are usually free amines, hydrochlorides, sulfates, p-toluenesulfonates, oxalates, phosphates, acetates, etc. Used in the form of.

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

Further, as a development accelerator, Japanese Patent Publication No. 37-1
No. 6088, No. 37-5987, No. 38-7826
Nos. 44-12380, 45-9019, and U.S. Pat. No. 3,813,247, thioether compounds, JP-A Nos. 52-49829 and 50-1555.
P-phenylenediamine compounds represented by No. 4, JP-A-50-137726, JP-B-44-30074,
Quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, and US Pat.
122 and 4119462, p-aminophenols, US Pat. Nos. 2,494,903 and 3,128,818.
No. 2, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, and the like, Japanese Patent Publication Nos. 37-16088, 42-2
5201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-
11431, 42-23883 and US Patent 35
Polyalkylene oxide represented by No. 32501,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

It is preferable that the color developing solution 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 and the like. The content of chlorine ions is 1.0 × 10 ^{−2 to} 1.5
× 10 ⁻¹ mol / liter is preferable, and more preferably 4 × 10 ⁻² to 1 × 10 ⁻¹ mol / liter. When the chloride ion concentration is more than 1.5 × 10 ⁻¹ mol / liter, it is not preferable for delaying the development and rapidly obtaining a high maximum concentration. On the other hand, if it is less than 1.0 × 10 ⁻² 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 bromine ion is preferably 3.
It is 0 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / liter, and more preferably 5.0 × 10 ^{−5 to} 5.0 × 10 ⁻⁴ mol / liter. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / liter, the development is delayed, the maximum concentration and sensitivity are lowered, and when the bromide ion concentration is lower than 3.0 × 10 ⁻⁵ mol / liter, stain is generated, and continuous treatment is performed. It is not preferable in that the photographic property variation (particularly the minimum density) is caused by the above.

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 brightener 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-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples thereof include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

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 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]. General formula [III]

[0065]

[Chemical 6]

Detailed description of the general formula [III] is described in Japanese Patent Application No.
It has the same meaning as the description of the general formula [E] described on pages 73 to 75 of the No. 178833 specification.

Exemplified Compounds of General Formula [III] III-1 to 45 The same as E-1 to 45 on pages 76 to 82 of the specification of Japanese Patent Application No. 2-178833.

The triazinyl stilbene type whitening agent can be synthesized by the usual method described on page 8 of "Fluorescent Whitening Agent" edited by Chemical Industry Association, published by August 1976.

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

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 N-methyl-p-aminophenol hexalphate (meth), phenidone, N, N'-diethyl-p-.
Aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 to 1.0 g / l.

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

For the color developing tank liquid, Japanese Patent Application No. 2-2
No. 40400, pages 69 to 74, the following general formula [K]
Chelating agents represented by and their exemplified compounds K-1 to K-
22 is preferably added from the viewpoint of effectively achieving the object of the present invention.

[0074]

[Chemical 7]

Among these chelating agents, especially K-
2, K-9, K-12, K-13, K-17, K-19
Is preferably used, and particularly when K-2 and K-9 are added to the color developing solution, the effect of the present invention is excellently exhibited.

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.

Further, the color developing tank solution may contain anionic, cationic, amphoteric and nonionic surfactants.

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 l 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 photosensitive material is 1 m ²
120 ml or less, more preferably 20 to 10
It is 0 ml.

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 a compound represented by the following general formula [I] is preferably used.

[0082]

[Chemical 10] [In the formula, A _{1 to} A ₄ may be the same or different, and
CH ₂ OH, represents a -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 aluminum). X has 3 to 3 carbon atoms
6 represents a substituted or unsubstituted alkylene group (eg, propylene, butylene, pentamethylene). The preferred specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0083]

[Chemical 11]

Other specific exemplified compounds include (A-2), (A-3), (A-5) to (A-5) described on pages 89 to 90 of Japanese Patent Application No. 274040/1990. -8),
(A-10) to (A-12) may be mentioned. Among them, I-1 is preferable.

These I-1, I-4, I-9, (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 [I] is preferably contained in an amount of 0.1 to 2.0 mol, and more preferably 0.15 to 1.5, per liter of the bleaching solution.
The amount is in the range of mol / liter, preferably in the range of 0.05 mol to 1.0 mol, and more preferably in the range of 0.1 to 0.5 mol / liter, per liter of the bleach-fixing solution. .

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 [I] 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 ferric complex salt of the compound represented by the general formula [I] accounts for 70% or more, more preferably 80% or more, and particularly preferably 90%.
% Or more, and most preferably 95% or more.

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, when the ammonium ion content is 30 mol% or less of all cations, the effect is remarkable.

In the present invention, the bleaching solution and the bleach-fixing solution include imidazole and its derivatives described in JP-A No. 64-295258 or the general formula [I] described in the specification.
To [IX] and at least one of these exemplified compounds can be effective for quickness.

In addition to the above accelerators, JP-A-62-1234
Example compounds described on pages 51 to 115 of the specification No. 59 and example compounds described on pages 22 to 25 of the specification of JP-A No. 63-17445, JP-A No. 53-956.
The compounds and the like described in JP-A No. 30 and JP-A No. 53-28426 can 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, antifoaming 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, it is used in the pH range of 6.0 to 8.5. The pH referred to here is the pH of the processing tank during the processing of the silver halide photosensitive material.

The temperature of the bleaching solution or the bleach-fixing solution is 20 ° C to 5 ° C.
It is preferably used at 0 ° C, preferably 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 processing bath and the storage tank of the processing replenisher, if desired, or a suitable method is used. An oxidizing agent such as hydrogen peroxide, bromate, persulfate or the like may be added as appropriate. Further, a member having a high oxygen permeability, such as silicone rubber, can be used as a pipe or the like 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 preferably at least 0.1 mol / liter in the tank liquid, more preferably
It is from 0.3 to 4 mol / liter, particularly preferably from 0.
It is 5 to 3 mol / 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, when the ammonium ion content is 30 mol% or less of all cations, the effect is remarkable.

The fixing solution may contain, in addition to the fixing agent, a pH buffering agent composed of various salts, alone or in combination of two or more kinds.
Furthermore, an alkali halide or ammonium halide,
For example, it is desirable to add a large amount of a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide. In addition, compounds known to be added to ordinary bleach-fixing solutions such as alkylamines and polyethylene oxides can be appropriately added.

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

To the bleaching solution, the fixing solution or the bleach-fixing solution, a compound represented by the following general formula [FA] described on page 56 of JP-A 64-295258 and its exemplified compounds may be added. .

[0101]

[Chemical 12]

The compound represented by the general formula [FA] described in the above specification can be prepared by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718. Can be synthesized. The above general formula [F
The compounds represented by A] may be used alone,
Moreover, you may use it in combination of 2 or more type.

Further, the compounds represented by the general formula (1) or (2) described in International Publication WO 91/08517, pages 5 to 10 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. To be

Further, it is also preferable to add the compound represented by the general formula [FA] or [FB] described in Japanese Patent Application No. 2-41549 and its exemplified compounds, and not only the effects of the present invention can be better exhibited. It is preferable for achieving ammonia free.

In the present invention, the replenishing amount of the fixing solution is preferably 900 ml or less per 1 m ² of the light-sensitive material, more preferably 20 to 750 ml. The temperature of the fixing solution is 20 ° C. to 50 ° C.
It is better to use at ℃, but preferably 25 ℃ ~ 45 ℃
Is.

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

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 minutes.
It is in the range of seconds to 3 minutes and 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 JP-A No. 1-206343 can be adopted. Further, in the present invention, a crossover time between tanks such as a color developing tank to a bleaching tank is within 11 seconds, preferably within 7 seconds, which is an effect different from that of the present invention. Further, a method of installing a duck hill valve or the like to reduce the processing liquid brought in by the light-sensitive material is also a preferable embodiment for carrying out the present invention.

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 for ferric ion, Japanese Patent Application No. 2-2347
No. 76, No. 1-324507, etc. are mentioned.

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

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 to 1.0 mol, and more preferably 0.002 to 2.0 mol, per liter of the stable tank liquid.

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

The stable tank liquid preferably contains a surfactant. As a surfactant, Japanese Patent Application No. 2-2
No. 74026, page 6 of the specification, water-soluble organic siloxane compounds represented by the general formula [II], and the same specification 67 to 67.
Exemplary compounds II-1 to 17 described on page 70 are mentioned,
Preferably II-1, II-3, II-7, II-1
3, II-15, II-16, II-17. Further, compounds represented by the general formulas [I] to [II] described in JP-A No. 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. Examples of such metal salts include Ba, Ca, Ce, Co, In and L.
a, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Z
There is a metal salt of r, Mg, Al or Sr, which can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate or a water-soluble chelating agent. The amount used is 1 × 10 ⁻⁴ to 1 per liter of stable tank liquid.
The range of ^{x10 -1} mol is preferable, and more preferably 4x.
It is in the range of 10 ^{−4 to} 2 × 10 ⁻² mol.

The stable tank liquid also contains organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) By-products 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 (JP-A-60-241053, 62-22541).
No. 51, JP-A-2-132440). 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 are 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, 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
No. 984 is described in detail.

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 further 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 15 to 70.
C. is preferable, and more preferably 20 to 55.degree.

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

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

Next, preferable photosensitive materials used in the present invention will be described.

When the light-sensitive material is a light-sensitive material for photographing, the silver halide grains have an average silver iodide content of 15 mol%.
The following silver iodobromide or silver iodochloride is preferably used, and silver iodobromide containing 4 to 15 mol% of silver iodide is particularly preferable. Among them, the average silver iodide content ratio preferable in the present invention is 5 mol% to 12 mol%, and most preferably 8 mol% to 11 mol%.

As the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The table below shows the locations.

[Item] [Page of RD308119] Iodine structure 993 IA Item Production method 993 I-A Item and 994 E Item Crystal habit Normal crystal 993 I-A Twin Crystal 〃 Epitaxial 〃 Halogen composition Uniform 993 IB Item Non-uniform 〃 Halogen conversion 994 IC Item 〃 Substitution 〃 Metal-containing 994 I-D Item Monodisperse 995 I-F Item Solvent addition 〃 Latent image forming position Surface 995 I-G Item 〃 Application Sensitive Negative 995 I -H item Positive (including internal fog particles) 〃 Used by mixing emulsions 995 I-J item Desalting 995 II-A item

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are Research Disclosure N
o. 17643, No. 18716 and No. 3081
19 (hereinafter RD17643 and RD18716, respectively)
And RD308119).

The locations described in the table below are shown. [Item] [Page of RD308119] [RD 17643] [RD 18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23 -24 648-9 Supersensitizer 996 IV-AE, J item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure. The following table shows the relevant locations. [Items] [Page of RD308119] [RD 17643] [RD 18716] Color turbidity inhibitor 1002 VII-I item 25 650 Whitening agent 998 V 24 UV absorber 1003 VIII C, XIII C item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Item

Various couplers can be used in the light-sensitive material used in the present invention, and specific examples thereof are described in the above-mentioned Research Disclosure. The following table shows the relevant locations.

[0131]

[Item] [Page of RD308119] [RD 17643] [RD 18716] Yellow coupler 1001 VII-D item VII C to G Magenta coupler 1001 VII-D item VII C to G cyan coupler 1001 VII-D item VII C to G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F alkali soluble coupler 1001 VII-E

The additive used in the present invention is RD3081.
It can be added by the dispersion method described in 19 XIV.

In the present invention, the above-mentioned RD17643, page 28, RD18716, pages 647-648 and RD.
The supports described in XIX of 308119 can be used.

For the photosensitive material, the above-mentioned RD308119 V is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section II-K can be provided. The photosensitive material is the RD described above.
308119 Various layer configurations such as a forward layer, an inverse layer, and a unit configuration described in the item VII-K can be adopted.

Next, another embodiment of the light-sensitive material used in the present invention will be described. That is, when the light-sensitive material is a color paper, silver halide particles mainly containing silver chloride containing at least 80 mol% of silver chloride are preferably used as the silver halide particles in the light-sensitive material, and more preferably. Those containing 90 mol% or more, particularly preferably 95 mol% or more, most preferably 99 mol% or more are used.

The silver halide emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol%.
The following is preferable, more preferably 10 mol% or less, still more preferably 3 mol% or less, and when silver iodide is present, 1 mol% or less is preferable, and more preferably 0.
It is 5 mol% or less, most preferably zero.

The silver halide grains mainly composed of silver chloride having a silver chloride content of 80 mol% or more may be applied to at least one silver halide emulsion layer, but preferably all of them are photosensitive. It is applied to a silver halide emulsion layer.

The crystals of the silver halide grains may be normal crystals, twin crystals or other crystals, and have the [1.0.0] plane and [1.
Any ratio can be used for the [1.1] plane. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, layers (phases) with different inside and outside
It may be in the shape of a core (core shell).
Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (JP-A-58-1)
No. 13934, Japanese Patent Application No. 59-170070). Further, silver halides described in JP-A 64-26837, 64-26838 and 64-77047 can be used.

Further, the silver halide grains are prepared by the acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing the silver halide grains, the pH, pAg and the like in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The color light-sensitive material processed in the present invention contains a color coupler in the silver halide emulsion layer.

The red-sensitive layer can contain, for example, non-diffusible color couplers which produce cyan partial color images, generally phenol or α-naphthol based couplers. The green-sensitive layer is, for example, at least one non-diffusible color coupler, usually 5 which produces a magenta partial color image.
-Pyrazolone color couplers and pyrazolotriazoles may be included. The blue-sensitive layer can include, for example, at least one non-diffusible color coupler that produces a yellow partial color image, typically a color coupler having open chain ketomethylene groups. For example, the color coupler is 6,
It can be a 4 or 2 equivalent coupler.

In the color light-sensitive material to which the present invention is applied, a 2-equivalent coupler is particularly preferable. Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilunglnausden Forschungslaboratorie).
n der Agfa), Leverkusen / Munich (Lever
kusen / Munchen), Vol.III .p.111 (1961)
"Color Coupler" (Farbkupple) by W. Pelz
r) ； K. Venkataraman, "The ・
Chemistry of Synthetic Soybean "(The C
hemirsry of Synthetic Dyes), Vol.4, 341-387, Academic Press, "The Theory of the Photographic Process" (The Theory)
of the Photographic Process), 4th edition, 353-362
Page; and Research Disclosure
losure) No. 17643, section VII. In particular, the magenta couplers represented by the general formula [M-1] as described on page 26 of JP-A-63-106655 (specific examples of these magenta couplers are JP-A-63-106655). , N on pages 29-34
o. 1-No. 77. ), A cyan coupler represented by the general formula [C-I] or [C-II] also described on page 34 (a concrete example of the cyan coupler is (C) described on pages 37 to 42 of the same specification). '-1) ~
(C'-82) and (C "-1) to (C" -36)), and high-speed yellow couplers described on page 20 (specifically exemplified yellow couplers 21 to 26 of the same specification). (Y'-1) to (Y'-39) described on page
Is preferable from the viewpoint of the effect of the object of the present invention.

Further, in order to more effectively achieve the object of the present invention, it is preferable to use a magenta coupler represented by the following general formula [MI] in the light-sensitive material for photographing or color paper. General formula [MI]

[0146]

[Chemical 38] In the magenta coupler represented by, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent. In the general formula [MI], the substituent represented by R is not particularly limited, but typically, each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples thereof include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, and the like.
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro compound residues, bridged hydrocarbon compound residues And so on.

The substituent represented by R, the group capable of splitting off by the reaction with the oxidation product of the color developing agent represented by X, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. Preferred ranges and specific examples of the substituents, and preferred ranges of the magenta coupler represented by the general formula [MI] are those described in EP-A-0327272, page 5, line 23 to page 8, line 52. Is the same as. The representative specific examples of the magenta coupler represented by the general formula [MI] are shown below.

[0150]

[Chemical Formula 39]

[0151]

[Chemical 40]

[0152]

[Chemical 41]

In addition to the representative examples described above, Japanese Patent Application No. 2-2
Among the compounds described on pages 63 to 82 of the specification of No. 18720, No. 13, 34, 42, 57-5
Of the compounds represented by 9, 61, 62, 65 to 67 and compounds described in European Patent Publication No. 0327272, pages 10 to 28, No. 3, 5-20, 22-33,
35-60, 62-77 and the same 02
Of the compounds described in No. 35913, pages 36 to 92, No. 1-4, 6, 8-17, 19-24, 2
6-43, 45-59, 61-104, 106-12
1,123-162,164-223 and the compound shown.

Further, the coupler is a Journal of the Chemical Society.
Society), Perkin I (1977), 2047-2052,
U.S. Pat. No. 3,725,067, JP-A-59-99437, JP-A-58-42045, JP-A-59-162548 and JP-A-5959.
-171956, 60-33552, 60-4
No. 3659, No. 60-172982, No. 60-1907.
79, 62-209457 and 63-3074.
It can be synthesized with reference to No. 53 and the like.

The above-mentioned couplers can be used in combination with other types of magenta couplers, and usually 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ³ mol per mol of silver halide.
It can be used in the range of ⁻² mol to 8 × 10 ⁻¹ mol.

When a nitrogen-containing phosphine ring-containing mercapto compound is used in a light-sensitive material using an emulsion mainly composed of silver chloride, not only the effect of the object of the present invention is satisfactorily achieved but also a bleach-fix solution is contained in a color developer. The effect on photographic performance that occurs when mixed,
Since it has another effect of making it extremely slight, it can be mentioned as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing dicyclic mercapto compounds are described in JP-A-63-106655,
Examples thereof include (I'-1) to (I'-87) described on pages 42 to 45.

The silver halide emulsions may be prepared by conventional methods (eg, constant inflow or double inflow with constant acceleration of the material). The adjusting method by the double inflow method while adjusting pAg is particularly preferable; Research Disclosure No. 17643, Sections I and II.

The silver halide emulsion can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, for example Belgian Patent 493,464.
And silver compounds as described in US Pat. No. 5,568,687, and polyamines such as diethylenetriamine according to Belgian Patent 547,323 or aminomethylsulfinic acid derivatives. Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium are also suitable sensitizers. This chemical sensitization method is described in the article by R. Kosiovsky (Z. Wiss. Photo.) 46 , 65-72 (1951) by R. Kosiovsky. Research Disclosure N above
o. See also 17643, Section III.

The emulsion mainly composed of silver chloride is an optically known method,
It can be sensitized with common polymethine dyes such as neutraocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like: FM Hamer's The Cyanine Dyes and rela
ted Compounds) (1964) Ullmanns Enz
yklpadie der technischen Chemie) 4th edition, 18 volumes, 4
31 and subsequent pages, and the above Research Disclosure No. See 17643, Section IV.

For the emulsion mainly containing silver chloride, conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer, preferably tetra- and pentaterazaindene, especially those substituted with hydroxyl or amino groups. Compounds of this kind are described, for example, in Birr's paper, Zeitschrift-Fur.
Bissen Schalich Photography (Z. Wiss. Ph
oto) 47, 1952, pp. 2 to 58, and Research Disclosure No. 17643, section IV.

The components of the light-sensitive material can be incorporated by a conventional known method; for example, US Pat. No. 2,322,027.
Nos. 2,533,514, 3,689,271, 3,764,336 and 3,765,897. The components of the light-sensitive material, such as couplers and UV absorbers, can also be included in the form of charged latex; DE-A 2,541,274.
And European Patent Application No. 14,921. The components can also be fixed in the light-sensitive material as polymers; for example German Patent Application Publication No. 2,044,992, US Pat. No. 3,370,952 and the same.
See No. 4,080,211.

As the support, it is preferable to use a reflective support such as baryta paper, polyethylene-coated paper or polypropylene goose paper.

Although the negative photosensitive material for photographing and the color paper among the photosensitive materials to which the present invention is applied have been described above, the photosensitive material to which the present invention is applied is not limited to these, and is also used for general or movie. There are color light-sensitive materials such as reversal film, color reversal paper and direct positive color paper, and black-and-white light-sensitive materials.

Next, as the automatic developing machine and the apparatus for supplying the solid processing agent preferably used for carrying out the processing method of the present invention, the apparatus described in the specification of Japanese Patent Application No. 3-141425 can be used.

[0166]

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

Example 1 A color development replenishing tablet for a color negative film was prepared according to the following procedure.

Operation (1) CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] 12 as a developing agent
Mill 0 g in an air jet mill until the average particle size is 10 μm. This fine powder is granulated by spraying 5.0 ml of water at room temperature for about 7 minutes in a commercially available fluidized bed spray granulator, and then the granulated product is dried at 63 ° 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 (2) 60 g of hydroxylamine sulfate are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed was 2.6 ml, and after granulation,
Dry at 60 ° C. for 7 minutes. Then granulate in vacuum at 40 ° C
And dried for 2 hours to almost completely remove the water content of the granulated product.

Operation (3) 58 g of sodium 1-hydroxyethane-1,1-diphosphonate, 70 g of sodium sulfite, 61 potassium carbonate
8 g, sodium hydrogen carbonate 30 g, sodium bromide 6
g and 40 g of diethylenetriamine pentaacetic acid are pulverized in the same manner as in the operation (1) and then uniformly mixed in a commercially available mixer. Next, in the same manner as in the operation (1), the amount of water sprayed is set to 200 ml and granulation is performed. After granulation, it is dried at 70 ° C. for 15 minutes, and then the granular material is dried in vacuum at 40 ° C. for 2 hours to almost completely remove water.

Operation (4) The granules prepared in the above operations (1) to (3) were treated at 25 ° C.
10 using a mixer in a room where the humidity is controlled to 40% RH or less.
Mix evenly for a minute. Next, 10 g of the compound shown in Table 1 is added and mixed for 5 minutes.

Using the commercially available hydraulic press machine and a mold having a diameter of 20 mm, the granular mixture thus obtained was filled at 5.0 g per tablet and the compression pressure at 700 kg / c.
The sample was made into m ² and compression-molded to prepare tablet samples 1-1 to 1-8 for color development replenishment for color negative film.

Experiment 1 After the above-mentioned tableting operation, the molded tablets were extracted using a hydraulic press machine, and the pressure necessary for extraction at this time was taken as the discharge pressure and measured using a load cell. This operation was repeated 10 times, and the average value was used as the discharge pressure.

Experiment 2 Ten tablet samples each obtained by the above operation were measured using a hardness tester (TS-50N manufactured by Okada Seiko Co., Ltd.), and the average value was taken as the hardness (strength) of the tablet sample. The results are shown in Table 1.

[0175]

[Table 1] In the table, PEG is polyethylene glycol.

As is apparent from Table 1, when the lubricant is not used, the obtained tablets have strength, but the discharge pressure is large and the lubricity is low. Further, magnesium stearate has a low discharge pressure and high lubricity, but the strength of the obtained tablet is low. On the other hand, it can be seen that the tablet of the present invention has large lubricity and strength.

Example 2 (Tablet for replenishing bleach for color negative) Operation (5) Ferric 1,3-propanediaminetetraacetic acid (PDTAF)
e) Grind and granulate 237 g of potassium monohydrate, 60 g of succinic acid, 73 g of maleic acid, and 10 g of 1,3-propanediaminetetraacetic acid in the same manner as in the operation (1). The amount of water spray is 5.
After making it 0 ml, it is dried at 60 ° C. for 7 minutes after granulation. 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) 100 g of sodium nitrate, 60 g of sodium bromide and 60 g of potassium carbonate are crushed and granulated in the same manner as in the operation (1).
The amount of water sprayed is 1.0 ml, and after granulation, it is dried at 70 ° C. 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 (7) The granulated product prepared in the above operation (6) was treated at 25 ° C. and 40% R
Mix evenly for 10 minutes using a mixer in a room whose humidity is controlled to H or less. Next, 6.0 g of the compound shown in Table 1 is added and mixed for another 5 minutes.

Using the commercially available hydraulic press and a die having a diameter of 28 mm, the granular mixture thus obtained was filled at a loading amount of 6.0 g per tablet and a compression pressure of 700 kg / c.
The mixture was compressed to m ² and compression-molded to prepare a bleach replenishing tablet sample for a color negative film.

When the above samples were used and evaluated in the same manner as in Example 1, similar results were obtained, confirming the effects of the present invention.

Example 3 (fixing replenishing tablet for color negative) Operation (8) Potassium thiosulfate 950 g, sodium thiocyanate 2
020g, sodium sulfite 120g, potassium carbonate 1
50 g, ethylenediaminetetraacetic acid disodium salt 10 g
Is pulverized and granulated in the same manner as in the operation (1). The amount of water spray is 3
After making it 0 ml, it is dried at 60 ° C. for 60 minutes after granulation. 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) was treated at 25 ° C. and 40% R
Mix evenly for 10 minutes using a mixer in a room whose humidity is controlled to H or less. Next, 32.5 g of the compound shown in Table 1 was added,
Mix for an additional 5 minutes.

Using the commercially available hydraulic press and a die having a diameter of 30 mm, the thus-obtained granular mixture was filled at a rate of 13.0 g per tablet and a compression pressure of 700 kg /
It was made into cm ² and compression-molded to prepare a fixing replenishing tablet sample for a color negative film.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, confirming the effects of the present invention.

Example 4 (Stable Replenishing Tablet for Color Negative) Operation (10) 200 g of m-hydroxybenzaldehyde, 1085 g of Emulgen 985; 45 g of potassium carbonate are pulverized and granulated in the same manner as in the operation (1). The amount of water sprayed is 3.0 ml, and 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 granules prepared in the above operation (10) are treated at 25 ° C. and 40%
Uniformly mix for 10 minutes using a mixer in a room whose humidity is adjusted to RH or less. Next, 2.65 g of the compound shown in Table 1 is added and mixed for another 5 minutes.

Using the commercially available hydraulic press and a mold having a diameter of 9 mm, the granular mixture thus obtained was filled at a loading amount of 0.3 g per tablet and a compression pressure of 700 kg / cm.
² was compression molded to prepare a tablet sample for stable replenishment for color negative film.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, confirming the effects of the present invention.

Example 5 (Table for color development replenishment for color paper) Operation (A) CD-3 [4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) developing agent ) Aniline sulphate] 100 g is ground in an air jet mill to an average particle size of 10 μm. This fine powder is granulated by spraying 4.5 ml of water at room temperature for about 5 minutes in a commercially available fluidized bed spray granulator, 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) In the same manner as in the operation (A), 185 g of diethylhydroxylamine oxalate is pulverized and granulated. The amount of water spray is 3.
After granulating to 0 ml, the mixture 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) 30.0 g of Tinopearl SFP (manufactured by Ciba Geigy), 3.7 g of sodium sulfite, 500 g of potassium carbonate, 0.3 g of potassium bromide, 25 g of diethylenetriamine-5-acetic acid.
g, 100 g of sodium p-toluenesulfonate and 200 g of potassium hydroxide are pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer.

Then, in the same manner as in the operation (A), the amount of water sprayed is set to 200 ml and granulation is carried out. , After granulation, granulate 7
Dry at 0 ° C. for 15 minutes, then dry the granulation in vacuum at 40 ° C. for 2 hours to remove almost completely the water of the granulation.

Operation (D) The granules prepared in the above operations (A) to (C) are treated at 25 ° C.
10 using a mixer in a room where the humidity is controlled to 40% RH or less.
Mix evenly for a minute. Next, 11.4
g and mix for an additional 5 minutes.

Using the commercially available hydraulic press and a mold having a diameter of 50 mm, the granular mixture thus obtained was filled at a rate of 5.8 g per tablet and a compression pressure of 700 kg / c.
The sample was made into m ² and compression-molded to prepare a tablet sample for color development replenishment for color paper.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, and the effect of the present invention was confirmed.

Example 6 (bleach-fix replenishing tablet for color paper) Operation (E) Ethylenediaminetetraacetic acid ferric sodium monohydrate 550
g and 20 g of ethylenediaminetetraacetic acid are pulverized and granulated in the same manner as in the operation (A). 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) 1770 g of potassium thiosulfate, 200 of sodium sulfite
g, potassium bromide 60 g, P-toluenesulfinic acid 2
0 g is crushed and granulated in the same manner as in the 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) to (F) are treated at 25 ° C.
10 using a mixer in a room where the humidity is controlled to 40% RH or less.
Mix evenly for a minute. Next, 26.6 of the compounds shown in Table 1
g and mix for an additional 5 minutes.

Using the commercially available hydraulic press and a die having a diameter of 40 mm, the granular mixture thus obtained was filled at a rate of 21.3 g per tablet and a compression pressure of 700 kg /
The sample was made into cm ² and compression-molded to prepare a bleach-fix replenishing tablet sample for color paper.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, confirming the effects of the present invention.

Example 7 (tablet for stable replenishment of color paper) Operation (H) 10 g of potassium carbonate, 1-hydroxyethane-1,1-
200 g of sodium diphosphonate, similar to the operation (A),
Pulverize and granulate. The amount of water sprayed is 1.0 ml, and after granulation, it is dried at 70 ° C. for 3 minutes. Then granulate 4 in vacuum
The granulated product is dried at 0 ° C. for 2 hours to almost completely remove water.

Operation (I) Chinopearl SFP 150 g, sodium sulfite 300
g, zinc sulfate heptahydrate 20 g, ethylenediaminetetraacetic acid 1
50 g are pulverized and granulated in the same manner as in the operation (A). The amount of water sprayed is 10.0 ml, and after granulation, 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.

The granules prepared by the above operations (H) to (I) are uniformly mixed for 10 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, 8.3 g of the compound shown in Table 1 is added and mixed for another 5 minutes.

Using the commercially available hydraulic press and a mold having a diameter of 9 mm, the thus-obtained granular mixture was charged at a loading amount of 0.66 g per tablet and a compression pressure of 700 kg / c.
The mixture was compressed to m ² and compression-molded to prepare a tablet sample for stable replenishment for color paper.

When the above samples were used and evaluated in the same manner as in Example 1, the same results were obtained, confirming the effects of the present invention.

Example 8 A method of processing a light-sensitive material using an automatic developing machine will be described below.

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 treatment experiment was performed. The table below shows the standard processing conditions for the automatic processing machine.

[0209]

[Table 2] The stabilizer is replenished in the third tank, and the overflow solution is sequentially flown into the second tank to the first tank.

Preparation of the automatic processing liquid was carried out by the following method. Color development tank liquid (21.0 liters) 15 liters of warm water at 35 ° C. was placed in the color development tank, and 399 color development replenishing tablets for color negative film prepared in the same manner as in Example 1 were charged and dissolved. Next, 21 starters of the following formulation, which were separately tabletted as starter components, were added, and after dissolution, 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 hydrogen carbonate 3.0 g potassium carbonate 0.5 g

Bleaching solution (5.0 liters) 3.0 liters of warm water at 35 ° C. was placed in a bleaching tank, and 350 bleaching replenishing tablets for color negative film prepared in the same manner as in Example 2 were charged and dissolved. Next, 10 starters of the following formulation, which were separately tabletted as starter components, were added, and after dissolution, warm water was added up to the tank mark to complete the tank solution.

Bleaching starter for color negative Sodium bromide 10 g Sodium hydrogen carbonate 1.5 g Potassium carbonate 3.5 g

Fixing solution (4.5 liters in the first tank, 4.5 liters in the second tank) Fixing tanks 1st and 2nd tanks each had hot water at 35 ° C. of 3.0.
Into a liter, 112 fixing replenishing tablets for color negative film prepared in the same manner as in Example 3 were charged and dissolved. Next, hot water was added up to the tank mark 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 4 by adding 3.0 liters of hot water at 35 ° C. to the first tank and the second tank of the automatic developing machine stabilizing tank, respectively. Add 40 tablets for stable replenishment for color negative film,
Dissolved. Next, hot water was added up to the tank mark to complete the tank solution.

Next, during the temperature control of the automatic developing machine, 20 tablets of the respective supplemental tablets prepared in Examples 1 to 4 were set in the supplemental tablet supplying device provided to the automatic developing machine.

This replenishing tablet is loaded one by one when two 135 size 24 film films are processed, and at the same time, 40 ml of replenishing warm water is supplied from the warm water supply device to the color developing tank.
The bleaching tank was set to supply 10 ml, the fixing tank to 40 ml, and the stabilizing tank to 80 ml.

The thus-prepared automatic developing machine was continuously treated with 100 pieces of exposed Konica color negative film DD400, Fuji color negative film SHG400 and Kodak color negative film gold 400 for 30 days each day.

After the continuous processing, Konica Color Negative Film Control Strip CNK-4 is processed,
The state of scratches on the film was observed.

After continuous treatment, the condition of contamination of each tank roller of the automatic developing machine was observed.

Furthermore, the generation of precipitates in the fixing tank was observed.

The results are shown in Table 3.

[0223]

[Table 3]

[Evaluation Criteria] Scratches on the film ◯: Not observed at all x: Many observed

Dirt on the roller part ◯: No deposits or deposits are seen Δ: Some deposits are seen ×: Many deposits or deposits are seen

Occurrence of precipitates ◯: Many precipitates are not seen Δ: Some precipitates are seen ×: Many precipitates are seen The larger the number ×, the larger the amount of precipitates.

From Table 3 above, the continuous processing using the processed tablet of the present invention is excellent in that the processed photosensitive material is free from scratches, the processing tank is less contaminated with rollers, and the fixing tank is free from precipitation. You can see that

Example 9 Konica Color Paper Type QA Processor-CL-P
The tablet supply function, the liquid level detection function, the hot water supply function, and the like were remodeled and provided on P-718, and the following treatment experiment was performed.
The table below shows the standard processing conditions for the automatic processing machine.

[0229]

[Table 4] The stabilizer is replenished in the third tank, and the overflow solution is sequentially flown into the second tank to the first tank.

Preparation of the automatic processing liquid was carried out by the following method. Color developing tank liquid (23.01) 18 liters of warm 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 5 were charged. , Melted. Next, 23 starters of the following formulation, which had been separately tabletted as starter components, were added, and after dissolution, warm water was added up to the tank mark to complete the tank solution.

Color developing starter for color paper Potassium chloride 4.0 g Potassium hydrogen carbonate 4.8 g Potassium carbonate 2.1 g

Bleach-fixing solution (23.01) 15 liters of warm water at 35 ° C. was placed in a bleach-fixing tank for an automatic developing machine, and 450 bleach-fixing replenishing tablets for color paper prepared in the same manner as in Example 6 were charged. , Melted. After dissolution, warm water was added up to the tank mark to complete the tank solution.

Stabilizer (15 liters for each of the 1st to 3rd tanks) Prepared in the same manner as in Example 7 by adding 12 liters of hot water at 35 ° C. to the 1st, 2nd and 3rd tanks of the automatic developing machine stabilizing tank. 60 tablets for stable replenishment for the color paper thus prepared were added and dissolved. Next, hot water was added up to the tank mark to complete the tank solution.

Next, during the temperature control of the automatic developing machine, 20 tablets of the respective supplemental tablets prepared in Examples 5 to 7 were set in the supplemental tablet supplying device provided to the automatic developing machine.

This supplemental tablet was manufactured by Color Paper 3200.
cm ² was added one by one, and at the same time, 51.2 ml of replenishing warm water was supplied from the warm water supply device to the color developing tank, 51.2 ml to the bleach-fixing tank, and 80 ml to the stabilizing tank. .

Konica Cara Paper QA-A5 was continuously treated with 5 m ^{2 for} 30 days on the automatic developing machine thus prepared.

After the continuous processing is completed, the Konica color paper
The control strip CPK-2-20 was treated, and the appearance of scratches on the color paper was observed.

As a result, the same result as in Example 8 was obtained.

Example 10 In Example 9, the exposed Konica color paper QA-
The same treatment was performed except that A5 was continuously treated for 20 m ² every day for 90 days.

After the completion of continuous processing, the presence or absence of precipitates in the bleach-fixing tank of the automatic developing machine was observed. The results are shown in Table 5.

[0241]

[Table 5]

[Evaluation Criteria] Precipitating Situation ◯: Many precipitates are not seen Δ: Some precipitates are seen ×: Many precipitates are seen × The larger the number of ×, the larger the amount of precipitates Indicates that.

As is clear from Table 5 above, the continuous treatment using the treated tablets of the present invention is satisfactory without the occurrence of precipitates.

[0244]

According to the present invention, a processing agent which is excellent not only in lubricity but also in strength can be obtained, and the film is not scratched during the processing of the light-sensitive material. It is possible to provide a solid processing agent for silver halide photographic light-sensitive materials, which does not cause stains on the parts, and also does not cause precipitation in the fixing tank or the bleach-fixing tank.

Claims (3)

[Claims] 1. A solid processing agent for a silver halide photographic light-sensitive material, which is obtained by tableting a processing agent containing at least one water-soluble lubricant. 2. A water-soluble lubricant is boric acid, DL-leucine, fatty acid alkali metal salt, lauryl sulfate alkali metal salt, benzoic acid alkali metal salt, adipic acid, fumaric acid,
The solid processing agent for a silver halide photographic light-sensitive material according to claim 1, which is at least one selected from sodium sulfate and polyethylene glycol. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the water-soluble lubricant is at least one selected from lauryl sulfate alkali metal salts, benzoic acid alkali metal salts, and polyethylene glycol. Solid processing agent