JPH08110617A - Solid fixing agent for silver halide photographic sensitive material and processing method - Google Patents

Abstract

PURPOSE: To sufficiently dissolve a solid fixing agent even in the case of successive processings short in the interval between each of 2 serial processings and to obtain good dryability by using a fixing agent in a solid state and incorporating aluminum ions in the form of a complex. CONSTITUTION: The fixing agent to be used for the silver halide photographic sensitive material is incorporated in a solid form and the aluminum ions are added in the form of a complex. In this case, the complex is an atomic group formed by combining one or more metal atom as a central atom with the other atom or atomic group (ligands). It is preferred to use as the main fixing agent, sodium, ammonium, and potassium thiosulfates, as a preservative, and the fixing solution may contain a surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid fixing agent for silver halide photographic light-sensitive materials, which dissolves quickly and has a stable fixing hard film, and a processing method using the same. In particular, the present invention relates to a solid fixing agent for silver halide photographic light-sensitive materials, which has good dryability when used in an automatic processor and has excellent suitability for rapid processing, and a processing method using the same.

[0002]

2. Description of the Related Art At present, many processing agents for silver halide photographic light-sensitive materials are sold as concentrated solutions which can be simply diluted and used. However, since this concentrated liquid is heavy and has a large volume, there has been a great demand for improvement in transportation cost and work efficiency. As a means for solving this, use of a solid processing agent has recently been proposed. This is different from the conventional solid powder treatment agent which is previously dissolved in water and prepared as a replenisher, in which the solid treatment agent is directly charged into the treatment tank according to the treatment amount. By adopting such a form, the solid processing agent can reduce the amount of the packaging material used and is preferable from the viewpoint of the environment. However, it has been a problem that it takes time to dissolve.

In recent years, in particular, a silver halide photographic light-sensitive material for medical use is desired to have a rapid processing property, and a stable performance in an extremely rapid processing of 30 seconds in Dry To Dry is required.

In the conventional solid fixing agent, it took a long time to dissolve in water, and when the treatment was carried out while the dissolution was insufficient, the concentration of aluminum ions was low and a sufficient fixing hardened film could not be obtained. If a sufficient fixing hard film cannot be obtained, the amount of water brought into the photosensitive material is large, and the drying load increases, which is not preferable for rapid processability.

When the hard film of the light-sensitive material is hardened as a means for improving the drying property, the developing property is deteriorated and the rapid processing property is deteriorated. In addition, there is another method of reducing the amount of the binder of the photosensitive material, but this method causes a remarkable generation of roller marks due to the pressure of the conveying roller of the automatic developing machine, which causes deterioration of the image and is substantially difficult.

On the other hand, if the hardened film varies depending on the state of dissolution of the fixing agent, it is not preferable in the conventional automatic developing machine using only hot air drying, because frame-like unevenness occurs in the photosensitive material.

Therefore, a solid fixing agent for a silver halide photographic light-sensitive material having a short fixing time and a stable fixing hard film, and a method for treating a silver halide photographic light-sensitive material having good drying property using the solid fixing agent are provided. Was wanted.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a solid fixing agent for silver halide photographic light-sensitive materials, which requires a short time for dissolution and has a stable fixing hard film, and a processing method using the same. Is. In particular, it is an object of the present invention to provide a solid fixing agent for a silver halide photographic light-sensitive material, which has good drying property when used in an automatic processor and is excellent in rapid processing suitability, and a processing method using the same.

[0009]

The present invention provides (1) a fixing agent for a silver halide photographic light-sensitive material, wherein the fixing agent is a solid fixing agent and contains aluminum ions in the form of a complex. A silver halide photographic light-sensitive material fixing agent, (2) a developing tank filled with a developing solution, and a method of continuously processing a silver halide photographic light-sensitive material in a development processing apparatus including a fixing tank filled with a fixing solution, A silver halide characterized in that a solid fixing agent containing a complex is directly replenished and added to the above-mentioned fixing tank or a fixing replenishing tank for introducing a processing solution from the fixing tank in accordance with the processing amount of the silver halide photographic light-sensitive material. (3) A method for processing a photographic light-sensitive material, wherein the time from the start of immersion of the silver halide photographic light-sensitive material in a developing solution to the end of drying is 30 seconds or less.
A method for processing a silver halide photographic light-sensitive material described in (4)
The method for processing a silver halide photographic light-sensitive material as described in (2) or (3) above, wherein the silver halide photographic light-sensitive material is processed by an automatic processor using infrared radiation drying in the drying step. ) A method of processing a silver halide photographic light-sensitive material as described in the above item (2) or (3), wherein the silver halide photographic light-sensitive material is processed by an automatic processor equipped with a heat roller in the drying step. Achieved by

The present invention will be described in detail below.

The complex referred to in the present invention is one in which one or more metal element atoms are central atoms, and other atoms or atomic groups (ligands) are bonded to them to form one atomic group. There is something. Further, all the ligands of the complex referred to in the present invention do not become H ₂ O, and the hydrate does not correspond to the complex referred to in the present invention.

Specific examples of the aluminum complex are shown below, but the invention is not limited thereto.

[0013] (a-1) Al [N (SiMe _{3) 2] 3} (a-2) _{[Al 3 0 (MeCOO) 6 (} H 2 O) 3 ] Cl (a-3) Na [Al (CH ₂ SiMe _{3) 4]} (a-4) [Al (NH _{3) 6]} Cl ₃ (a-5) [Al (CN) _6] Cl ₃ where Me represents a methyl group.

As the fixing agent base of the present invention, sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate are preferable, and ammonium thiosulfate is particularly preferable.

The concentration of thiosulfate as the fixing solution is preferably 0.1 to 5 mol / liter, more preferably 0.1.
It is 3 to 2 mol / liter, more preferably 0.5 to 1.
It is 5 mol / liter.

The fixing agent of the present invention preferably contains a sulfite as a preservative, and the concentration of the sulfite is 0,0 when dissolved and mixed with thiosulfate and sulfite in water.
It is 2 mol / liter or less, preferably 0.1 mol / liter or less. As the sulfite, potassium, sodium, ammonium salts and the like are used, and the fixing solution preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid, and optical isomers thereof. Examples of the salt include potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate, sodium tartrate. Preferred examples include lithium, potassium, sodium, and ammonium salts represented by potassium, sodium malate, ammonium malate, sodium succinate, ammonium succinate, and the like. Only together can be used.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, etc. are supplied as solids and used by dissolving them in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / liter or more, and the most preferred content is 0.2-
It is 0.6 mol / liter.

The pH of the fixing solution is preferably 3.8 to 5.8, particularly preferably 4.5 to 5.1. It should be noted that the higher the pH, the higher the fixability but the dryness deteriorates.

The processing conditions of the fixing solution of the present invention are preferably a fixing time of 5 to 20 seconds, a processing temperature of 15 to 45 ° C., and particularly preferably 25 to 38 ° C.

A surfactant may be added to the fixing solution of the present invention. Preferred surfactants include, for example, anionic surfactants such as sulfate ester and sulfonate, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Can be mentioned.

The fixer contains various acids in addition to the above compounds.
Additives such as salts, chelating agents and wetting agents can be included.

Examples of the acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferable. The preferable addition amount of the additive is 0.5 to 20 g / liter.

The fixing agent used in the present invention is described in JP-A-4-13.
0431, 4-143756, 4-143757, 4-229860,
4-170539, 5-34872, 3-101728, 4-23074
No. 9, No. 5-66540, No. 5-72696, No. 5-119445, No. 5-8
The compounds described in No. 0450 can be used.

The solid fixing agent of the present invention is a solid processing agent such as the above-mentioned powder processing agent, tablets, pills and granules, which is optionally moisture-proofed.

The powder in the present invention refers to an aggregate of fine grain crystals. The granules referred to in the present invention are those obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. The tablet referred to in the present invention refers to a tablet obtained by compression-molding powder or granules into a given shape.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is preliminarily formed on the surface of the photographic processing agent. It is possible to employ any means such as forming a coating layer by spraying (Japanese Patent Laid-Open No. 4-29136, 4-85535,
4-85536, 4-85533, 4-85534, 4-172341).

A preferable tablet manufacturing method is a method in which a powdery solid processing agent is granulated and then a tableting step is performed to form the tablet. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crush granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like are used. Can be done.
For tablet formation, the average particle size of the obtained granules is 100-800 μm in that when the granules are mixed and compressed under pressure, the components become nonuniform, so-called segregation does not easily occur. It is preferable to use one, more preferably 200 to 750 μm
Is. Furthermore, the particle size distribution is ± 10 for 60% or more of the granulated particles.
Those within a deviation of 0 to 150 μm are preferred. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effects become more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

A method for producing a tablet treating agent is described in, for example, Japanese Patent Laid-Open No.
51-61837, 54-155038, 52-88025, British patent
It can be produced by a general method described in the specification such as 1,213,808, and the granule treating agent is, for example, JP-A-2-09042.
No. 2, No. 2-09043, No. 3-39735, and No. 3-39739, etc. Further, the powder processing agent is, for example, JP-A-54-133332, British Patent 7
It can be produced by a general method as described in the specifications such as 25,892, 729,862 and German Patent 3,733,861.

The bulk densities of the above solid processing agents are tablets in view of their solubility and the effects of the object of the present invention.
In terms of the strength of 1.0g / cm ³ ~2.5g / cm ³ is preferably 1.0 g / cm ³ greater than the resulting solid, from the viewpoint of solubility of the solid product obtained as 2.5 g / cm ³ less than preferable. When the solid processing agent is granules or powder, the bulk density is 0.40 to 0.95g
/ Cm ³ is preferable.

It is within the scope of the present invention to solidify only one part of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. is there. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the processing tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. The replenishing water tank may be placed outside or may be built in the automatic developing machine, and it is preferable to install the replenishing water tank from the viewpoint of space saving.

When the developer is solidified, all the alkali agents and reducing agents should be solid processing agents, and in the case of tablets, at least 3 agents and most preferably 1 agent should be used. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

The package of the solid processing agent of the present invention can be carried out using the following materials.

As the synthetic resin material, polyethylene (either high pressure method or low pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyester, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (polymer described in JP-A-63-63037, JP Any of the polymers described in JP-A-57-32952) may be used. Alternatively, pulp may be used.

Although these are preferably made of a single material, when they are used as a film, the films are laminated and adhered, but they may be used as a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films such as using aluminum foil or aluminum vapor deposition synthetic resin between the above synthetic resin films.

In addition, the oxygen permeability of these packaging materials is 50 ml / m ^{2 in} order to maintain the solid processing agent and prevent the generation of stains.
24hr ・ atm or less (at 20 ℃ 65% RH), more preferably 30ml /
It is preferably m ² 24 hr · atm or less.

The total thickness of these laminated films or single layers is preferably 1 to 3000 μm, more preferably 10 to 2000 μm, and further preferably 50 to 1000 μm.

The above synthetic resin film may be a single layer (polymer) resin film, or a laminate of two or more (polymer)
It may be a resin film.

Examples of the one-layer polymer resin film satisfying the conditions of the present invention include (1) polyethylene terephthalate (PET) having a thickness of 0.1 mm or more, and (2) acrylonitrile butadiene copolymer having a thickness of 0.3 mm or more. (3) Hydrochloric acid rubber having a thickness of 0.1 mm or more, and the like. Among them, polyethylene terephthalate is excellent in alkali resistance and acid resistance.
It can be preferably used in the present invention.

Next, as a laminated polymer resin film which meets the conditions of the present invention, for example, (4) PET / polyvinyl alcohol / ethylene copolymer (Eval) / polyethylene (P)
E), (5) oriented polypropylene (OPP) / Eval / PE,
(6) Unstretched polypropylene (CPP) / Eval / PE,
(7) Nylon (N) / Aluminum foil (Al) / PE, (8) PET / A
l / PE, (9) cellophane / PE / Al / PE, (10) Al / paper / PE, (11) PET / PE / Al / PE, (12) N / PE / Al / P
E, (13) Paper / PE / Al / PE, (14) PET / Al / PET / Polypropylene (PP), (15) PET / Al / PET / High Density Polyethylene (HDPE), (16) PET / Al / PE / low density polyethylene
(LDPE), (17) Eval / PP, (18) PET / Al / PP, (1
9) Paper / Al / PE, (20) PE / PVDC coated nylon / PE /
Ethyl vinyl acetate / polyethylene condensate (EVA),
(21) PE / PVDC coated N / PE, (22) EVA / PE / aluminum deposited nylon / PE / EVA (23) Aluminum deposited nylon / N / PE / EVA (24) OPP / PVDC coated N / PE, (25 ) PE / PVDC coat N
/ PE, (26) OPP / Eval / LDPE, (27) OPP / Eval / CPP, (28) PET / Eval / LDPE, (29) ON (stretched nylon) / Eval / LDPE, (30) CN (unstretched) Nylon) / Eval / LDPE, etc., among which (20) to (3
0) is preferably used.

As a more specific structure of the packaging material, if the side in contact with the treatment agent is the inner surface, PE / mainly paperboard / PE / Al / epoxy-phosphoric acid resin layer / polyester resin in this order from the inner surface. Layer / PE PE / K-Nylon / PE or adhesive / Al / PE / paperboard / PE, PE / vinylon / PE or adhesive / Al / PE / paperboard / PE PE / vinylidene chloride / PE or adhesive / Al / PE / Paperboard /
PE PE / polyester / PE or adhesive / Al / PE / paperboard / PE polypropylene / K-nylon / polypropylene / Al / polypropylene / paperboard / polypropylene.

As a method for moisture-proof packaging of tablets and granules, there is a 4-way seal, 3-way seal stick (pillow package, gusset package) PTP cartridge.

The four-way seal, the three-way seal, and the stick (pillow, gusset) packaging have different forms, and the above materials are used. However, when using the peel open method, a sealant agent is laminated to give the peel open aptitude.

The peel-open method generally includes a cohesive failure method, an interfacial peeling method, and an interlayer peeling method.

The cohesive failure method is an adhesive called hot melt, which is used as a sealant in a heat seal lacquer, and peels off due to internal cohesive failure of the sealant layer at the time of opening.

The surface-active peeling method is a method of peeling at the interface between films, in which the sealing film (sealant) and the adherend are not completely fused and can be peeled off with appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene or a copolymer thereof, polyester, or the like can be selected depending on the material of the adherend.

Further, a delamination method is one in which a sealant is peeled between layers of a laminated film by using a multilayer coextrusion film such as a laminated film.

In the peel open method using the film of the present invention, the interlaminar peeling method or the interfacial peeling method is preferable.

Since such a sealant is thin,
Usually other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester
(Polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum, etc. are laminated and used, but polyethylene, polypropylene, polyester, eval and the like are preferable in consideration of moisture resistance, environmental friendliness and matching with contents. In consideration of printability, the outermost surface is preferably made of unstretched polypropylene polyester or paper.

As the sealant film, for example, Tohcello, CMPS film, Dainippon Ink Diffran PP
-100, PS-300 or letterpress printing LTS film, San-A Chemicals Sunseal FR, Sunseal MS, etc., and those already laminated with polyester include Declan C-1600T, C-1602T.

PTP is a type of blister pack that is molded into P
It is a packaging form in which a solid processing agent is put into a sheet such as VC or CPP and heat-sealed with an aluminum sealing material.

Environmentally, PVC is not used as a forming material, and recently A-PET and highly moisture-proof PP (eg TAS-1130, TAS-2) are used.
230, TAS-3230: Taisei Kako Co., Ltd. is preferably used.

When the treating agent is packaged or bound or coated with a water-soluble film or a binder, the water-soluble film or the binder may be a polyvinyl alcohol type, a methyl cellulose type, a polyethylene oxide type, a starch type, a polyvinyl pyrrolidone type, Hydroxypropyl cellulose type, pullulan type, dextran type and gum arabic type,
Polyvinyl acetate type, hydroxyethyl cellulose type, carboxyethyl cellulose type, carboxymethyl hydroxyethyl cellulose sodium salt type, poly (alkyl)
Films or binders composed of oxazoline-based or polyethylene glycol-based substrates are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of the effect of coating or binding.

The preferred polyvinyl alcohol is a very good film-forming material and has good strength and flexibility under most conditions. Commercially available polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but have molecular weights of about 10,000 to about 10,000.
It is preferably 0. The degree of hydrolysis is the rate at which the acetic acid ester group of polyvinyl alcohol is replaced with a hydroxyl group. For film applications, the range of hydrolysis is usually from about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.

The method for producing these water-soluble films is described in, for example, JP-A-2-124945, JP-A-61-97348, and JP-A-60-15824.
No. 5, JP-A-2-86638, JP-A-57-117867, JP-A-2-7
No. 5650, JP-A-59-226018, JP-A-63-218741, and JP-A-54-1
It is produced by a general method as described in the specification of No. 3565 and the like.

Further, these water-soluble films are solvulon.
(Manufactured by Aicero Chemical Co., Ltd.), Hi-Selon (manufactured by Nigo Film Co., Ltd.)
Alternatively, a commercially available product under the name of pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, Chris Craft Industries Inc.'s MONO-SOL
The 7-000 series polyvinyl alcohol film available from the department dissolves at a water temperature of about 34 ° F. to about 200 ° F., is harmless and exhibits a high degree of chemical resistance, and is particularly preferably used.

The thickness of the above water-soluble film is preferably 10 to 120 μ, particularly 15 to 80 μ in terms of storage stability of the solid processing agent, dissolution time of the water-soluble film, and crystal precipitation in an automatic processor. Preferred, especially 20
Those having a size of -60 μm are preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellently achieved.

Furthermore, the tensile strength of the water-soluble film is 0.5.
× 106 to 50 × 106 kg / m ² is preferable, and particularly 1 × 106 to 25 × 1
06 kg / m ² is preferable, especially 1.5 × 10 6 to 10 × 10 6 k
g / m ² is preferred. These tensile strengths are measured by the method described in JIS Z-1521.

Further, a photographic processing agent packaged or bound or coated with a water-soluble film or a binding agent is used in storage, transportation, and handling during storage, transportation, and handling, such as high humidity, atmospheric humidity such as rain and fog, and water. It is preferably packaged in a moisture-proof packaging material in order to prevent damage from accidental contact with water due to splashing or wet hands, and the moisture-proof packaging material has a film thickness of 10 to 150 μm.
Film is preferable, and the moisture-proof packaging material is a polyolefin film such as polyethylene terephthalate, polyethylene, and polypropylene; kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, and polyvinyl chloride that can have a moisture-proof effect with polyethylene. It is preferably at least one selected from a metal foil such as vinylidene, polyamide, polycarbonate, acrylonitrile and aluminum, and a metallized polymer film, or a composite material using these.

In the practice of the present invention, it is also preferable that the moisture-proof packaging material is a degradable plastic, particularly a biodegradable or photodegradable plastic.

Examples of the biodegradable plastic include natural polymers, polymers produced by microorganisms, synthetic polymers with good biodegradability, blending of biodegradable natural polymers with plastics, and photodegradable plastics are , Those having a group which is excited by ultraviolet rays and which is linked to cleavage exist in the main chain. Further, other than the above-mentioned polymers, those having two functions of photodegradability and biodegradability at the same time can be favorably used.

The specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Microorganism-produced polymer PHB-PHV (3-hydroxybutyrate and 3-hydroxyvalerate). "Biopol" containing (copolymer with rate) as a component, microbial-produced cellulose and other biodegradable synthetic polymers polyvinyl alcohol, polycaprolactone, etc., or their copolymers or mixtures Biodegradable natural polymers into plastics As a natural polymer having good biodegradability, there are starch and cellulose, which are shape-disintegrating properties in addition to plastic.

Examples of photodegradability include introduction of a carbonyl group for photodisintegration, and an ultraviolet absorber may be added to accelerate disintegration.

Regarding such degradable plastic,
`` Science and Industry '' Vol. 64, No. 10, pp. 478-484 (1990),
“Functional materials”, generally described in July 1990, pp. 23-34, can be used. Also, Biopol
(Manufactured by ICI), Eco (manufactured by Union Carbide), Ecolite (manufactured by Eco Plastic), Ecostar (manufactured by Eco Star)
Commercially available degradable plastics such as t. 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 hr or less.

The development processing method of a silver halide photographic light-sensitive material according to the present invention comprises steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing (or stabilizing) and drying. Is preferably completed in 30 seconds or less.

That is, the time from the time when the tip of the photosensitive material starts to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry time) is 30 seconds or less. That is, more preferably, a remarkable effect can be seen when the Dry to Dry time is 10 seconds to 25 seconds.

As the drying method according to the present invention, a drying method using a heat roller or infrared radiation is used. The heat roller referred to in the present invention means a transport roller whose outer periphery is heated by a heat source, and a transport roller which has a heat source inside and whose outer periphery is heated is preferable.

The surface temperature of the infrared heater is 150 ° C to 260 ° C
Is preferred. Both drying methods may be used in combination. In addition, a conventional method of blowing warm air can be used together for both drying methods.

The line speed of the automatic developing machine according to the present invention is preferably 700 mm / min or more.

In the present invention, as a means for supplying the solid fixing agent to the fixing tank of the automatic developing machine, it is preferable to directly supply the solid fixing agent to the fixing tank of the automatic developing machine. At this time, water is replenished at the same time. Is preferred.

It is also possible to provide a fixing replenishing tank for introducing the processing liquid from the fixing tank and replenish and add the solid fixing agent to the replenishing tank.

Further, in the automatic developing machine of the type in which the solid processing agent is directly supplied to the processing tank, even when the driving of the photosensitive material conveying means is stopped after the development processing of the photosensitive material is completed, the processing is performed from the time of the stop. It is preferable that the pump is continuously driven for a predetermined period of time required for the agent to dissolve to circulate the treatment liquid. The solid fixing agent of the present invention has good solubility, and it is sufficient to drive the pump for 1 hour or less after the completion of development processing, and particularly preferably in the range of 10 seconds to 10 minutes. Among them, the range of 15 seconds to 1 minute is particularly preferable. If this time is too long, it is not preferable from various viewpoints such as usability, energy saving, deterioration of the processing solution and filter clogging.

In the present invention, as the supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Laid-Open Nos. 63-137783 and 63-97522,
Although there is a known method such as Japanese Utility Model Laid-Open No. 1-85732, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is a granule or powder, it is used in Japanese Utility Model Laid-Open Nos. 62-81964, 63-84151 and JP-A-1-
No. 292375, the gravity drop method described and No. 63-105159,
The method using screws or screws described in JP-A-63-195345 and the like is a known method, but is not limited thereto.

However, a preferable method is, as the supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which is previously weighed and divided and packaged is opened according to the processing amount of the photosensitive material, and the package is opened. A method of taking it out is possible. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably one replenishment amount, and the package is separated in two directions or the package A part of it is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous fall. A predetermined amount of the solid processing agent is housed in a package that is divided and hermetically sealed so that the air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, a configuration is conceivable in which a package composed of at least two packaging materials sandwiching the solid processing agent is closely adhered or adhered to each other so that the periphery of the solid processing agent can be separated. . By pulling the respective packaging materials sandwiching the solid processing agent in different directions, the closely contacted or adhered contact surfaces are separated, and the solid processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term "opening" as used herein means a cut or break that leaves a part of the packaging material. As the unsealing method, the solid processing agent is forcibly pushed out by applying a compressive force from the packaging body on the non-opening side to the packaging body which can be opened through the solid processing agent, or on the packaging body on the openable side. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting the processing amount information. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or opening based on the obtained supply start signal operates, and the driving means for separating or opening based on the supply stop signal is It can be controlled to stop.

The solid processing agent supply means has a control means for charging a fixed amount of the solid processing agent in accordance with information on the processing amount of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic developing machine of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance. What is the processing amount information of silver halide photographic light-sensitive materials?
It is a value proportional to the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, or the processing amount of the silver halide photographic light-sensitive material being processed. It indicates indirectly or directly the amount of reduction of the treating agent in the liquid. It may be detected before or after the photosensitive material is carried into the processing liquid, or at any timing during immersion in the processing liquid. Further, it may be a physical parameter such as the concentration of the composition in the treatment liquid or a change in the concentration, pH and specific gravity. Further, it may be the amount of the treatment liquid which is discharged to the outside after drying.

The solid processing agent of the present invention may be charged in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In general, the temperature of an automatic processor is adjusted, so that the temperature of the processing liquid is adjusted by an electric heater. As a general method, a heat exchange part is provided in an auxiliary tank connected to the treatment layer, a heater is installed, and a pump is arranged in this replenishment tank to feed the liquid from the treatment tank in a constant circulation amount and to keep the temperature constant. There is.

Usually, a filter is arranged for the purpose of removing the crystalline foreign matter that is mixed in the processing liquid or is generated by crystallization, and plays a role of removing the foreign matter.

The most preferable method is to put the solid processing agent in a place, such as this auxiliary tank, which communicates with the processing section and in which the temperature is adjusted. This is because the insoluble component in the processing agent that has been added is blocked from the processing section by the filter section, and it is possible to prevent solids from flowing into the processing section and adhering to the photosensitive material, etc. It will be good.

Further, when the treatment agent input portion is provided in the treatment tank together with the treatment portion, it is preferable to devise a shield or the like so that the insoluble portion does not come into direct contact with the film or the like.

As for the material of the filter and the filtering device, all materials used in general automatic developing machines can be used in the present invention, and the special structure and material do not influence the effect of the present invention.

The number of circulation of the treatment liquid circulated by the circulation means in the present invention is preferably 0.5 to 2.0 times / min, particularly 0.8 to 2.0 times / min, and further preferably 1.0 to 2.0 times / min. This accelerates the dissolution of the solid processing agent, and also
It is possible to prevent the formation of lumps of high-concentration liquid, the occurrence of uneven density of the processed photosensitive material, and the occurrence of insufficiently processed photosensitive material. Here, the number of circulations indicates the flow rate of the liquid to be circulated, and it is defined as once when the liquid amount corresponding to the total liquid amount in the processing tank flows.

The solid treating agent according to the present invention is added to the treatment tank separately from the replenishing water, and the replenishing water is supplied from the replenishing water tank.

The antifungal means of the refill water tank of the present invention will be described. If the exchange rate in the rehydration tank is reduced and the residence time of the water is prolonged, scales are generated, and after two to three weeks, there is a problem that the water rots and an odor is generated. Further, if the generated water scale is replenished as it is, it will adhere to the surface of the photographic light-sensitive material or the solid processing agent and cause development unevenness in the case of a developing tank and poor fixing in the case of a fixing tank, which will significantly reduce the commercial value. There is. Therefore, in order to remove this water stain, it has to be washed regularly, which is very troublesome. . Therefore, the water supply tank of the present invention has a fungicide. This antifungal means can be achieved by at least one means selected from the following group.

(Group) a. Chelating agent addition means b. Antifungal agent addition means c. Deionization treatment means d. Ultraviolet irradiation means e. Magnetic processing means f. Ultrasonic processing means g. Electrolytic sterilization means h. Silver ion releasing means i. Air bubbling means j. Active oxygen release means k. Means by contact with porous material l. Means for Preventing Growth of Harmful Bacteria by Adding Other Harmless Fungi These means will be specifically described. The chelating agents and bactericides used as antifungal means in this invention are LEWest
“Water Quality Criteria” Phot.Sci.and Eng., Vo19,
No. 6, pp. 398 (1965), ME Beach ”. Microbiological Growt
h in Motion-Picture Processing ”SMPTE Journal, vol.
85.mar. (1976), RODeegan, “Photoprocessing Wash W
ater Biocides ”J.Imaging Tech.vol.10, No.6, p.239 Dec
(1984), JP-A-57-8542, JP-A-58-105145, and JP-A-57-15724.
The compounds described in No. 4, No. 62-220951 and the like can be used.

Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), 2-hydroxy-4-sulfophenol and 2-hydroxy-3. 1,5-Disulfophenol is preferable, and as the bactericide, phenol compounds, thiazole compounds and benztriazole compounds are preferable. Specifically, 1,2-benzisothiazolin-3-one, 2
-Methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, o-phenylphenol sodium and benztriazole are preferable compounds. Can be mentioned. It is preferable that these compounds are in the form of tablets if they are packaged in a package, and if they are divided and weighed in advance, they are individually packaged in an amount to be added at one time.

The means for adding these may be added by hand by the pharmacist, but preferably the solid processing agent supply device of the present invention is installed, and the addition is carried out more preferably with a detector in the rehydration tank. From the viewpoint of maintenance-free, it is preferable to add water automatically when water is replenished up to a certain amount in the tank.

The means for reforming water with the ion exchange resin of the present invention can be carried out based on the means described in JP-A-61-131632.

As the ion exchange resin, various known cation exchange resins (strongly acidic cation exchange resin, weakly acid cation exchange resin) and various anion exchange resins (strongly basic) described in Public Technical Report, Japanese Patent No. 90-473, etc. Anion exchange resin), and these can be used alone or in combination. Usually, it is preferable to use a strongly acidic H type cation exchange resin and a weakly basic OH type anion exchange resin. It may be attached to the water replenishment tank or the water may be improved elsewhere.

As a preferable strong acid ion exchange resin,
DIAION SK1B SK102, SK104, SK106, SK110, SK112, SK11
6 (Mitsubishi Kasei Co., Ltd.) and preferred OH type strongly basic anion exchange resins are DIAION PA406, PA408, PA412, PA41.
6, PA418 (Mitsubishi Kasei Co., Ltd.).

The means for irradiating with ultraviolet rays of the present invention can be implemented by the means described in JP-A-60-263939. As the ultraviolet irradiation device, a product manufactured by Kindai Bio Research Institute (headquarters Kobe City) is small and can be preferably used. The means for applying the magnetic field of the present invention can be implemented by the means described in JP-A-60-263939. The means for applying ultrasonic waves of the present invention can be implemented by the means described in JP-A-60-263940. The means for applying the electrolysis of the present invention can be carried out by the means described in JP-A No. 3-22468. The means for releasing silver ions of the present invention include a means for putting a silver foil or a silver plate in a water replenishing tank, a means for coating the inner wall with silver, and a means for putting a silver ion releasing compound.

The air bubbling means of the present invention may be a very simple means for blowing bubbles into the replenishment water tank, and is appropriately selected according to the size of the replenishment water tank. From the viewpoints of compactness and economy, a, b, c, g, and h are preferable as means for preventing the generation of these scales and microorganisms, and more preferable are a,
c and h are selected.

The silver ion-releasing compound of the means h is an organic compound such as silver chloride, silver bromide, silver iodide, silver oxide, silver sulfate, silver nitrate, silver acetate, silver oxalate, silver behenate, and silver maleate. Specific examples include silver oxide.

These silver compounds use a SiO ₂ —Na ₂ O type glass body having a chemical structure as a base structure component, or a methane type SiO ₄ tetrahedron and an AlO ₄ tetrahedron that are 1 In the present invention, a zeolite body having a three-dimensional skeleton structure in which individual oxygen atoms are shared and containing the silver compound is preferably used.

These silver compounds, and the zeolite bodies and glass bodies containing the compounds can be obtained as commercially available products, for example, Bio-Sure SG manufactured by Kinki Pipe Giken Co., Ltd. Examples thereof include Opargent tablets manufactured by Opo Pharma (Switzerland) and Zeomic manufactured by Sinanen Zeomic Co., Ltd.

Further, the silver compound, the zeolite body and the glass body containing the compound according to the present invention can be used in various shapes. For example, it may be in the form of powder, spheres, pellets, fibers, or filters, or these may be kneaded into fibers such as cotton, wool, polyester, etc. before use. Specific examples thereof include SANITER 30 manufactured by Kuraray Co., Ltd. and the like.

Of these, the filter-like and spherical ones are one of the preferred embodiments in the present invention.

Furthermore, it is also one of the preferred embodiments of the present invention to use the silver compound or the zeolite or glass containing the compound in a water permeable container such as a plastic case or a tea bag. . In addition, Clinker 205 manufactured by Nichiban Kenkyusho Co., Ltd. or Pacific Chemical's rackin can also be preferably used.

The solid processing agent used in the present invention includes, as a binder, saccharides (monosaccharides, polysaccharides in which a plurality of monosaccharides are glycoside-bonded to each other, as described in Japanese Patent Application No. 6-91987 (pages 23 to 30)). Decomposition products) are preferred, and those selected from dextrins and sugar alcohols are particularly preferably used. There is little change in shape during long-term storage, troubles occur during addition, and usability is improved.

In the solid processing agent used in the present invention, it is preferable to use acylated amino acids described in Japanese Patent Application No. 5-186254 (pages 9 to 15) as lubricants. The solid processing agent can be stably produced without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved.

The solid treating agent used in the present invention contains a hydroxylamine, a phenylcarboxylic acid, a phenylsulfonic acid, a hydroxyl group or a carboxyl group described in Japanese Patent Application No. 6-70860 (pages 14 to 33) as a coating agent. It is preferable to use introduced alkyl (or alkenyl) carboxylic acids, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid-based betaine-type polymers, etc.), and saccharides. There is little generation of fine powder, little deterioration of solubility, excellent storage stability, and stable photographic performance can be maintained.

In the developer used in the present invention, in addition to dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232 (pages 19 to 20) as developing agents, JP-A-5-165161 is used. The described reductones are also preferably used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

As the preservative, in addition to the sulfite described in Japanese Patent Application No. 4-28632, an organic reducing agent can be used as the preservative. In addition, a chelating agent described in Japanese Patent Application No. 4-586323 (page 20) and a bisulfite adduct of a hardening agent described in the same (page 21) can be used. Also, as a silver sludge inhibitor, Japanese Patent Application No. 4-4929
No. 47, Japanese Patent Application No. 5-96118 (general formula [4-a] [4-b]
It is also preferred to add the compounds mentioned. Addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A 1-124853 are particularly preferable.

An amine compound may be added to the developer of the present invention, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

The developer used in the present invention requires the use of a buffering agent, and examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate and tripotassium phosphate. , Dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o-
Examples thereof include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

As the development accelerator, Japanese Patent Publication No. 37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And thioether compounds represented by U.S. Pat. No. 3,813,247, p-phenylenediamine compounds represented by JP-A-52-49829 and 51-15554, and JP-A-50-137726.
No., 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. 32-53919, 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, Japanese Patent Publications 41-11431, 42-23883 and U.S.A. If necessary, polyalkylene oxide represented by Patent 3,532,501 and the like, other 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles and the like can be added.

As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, As a typical example, a nitrogen-containing heterocyclic compound such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, a cyclodextrin compound and other compounds described in JP-B-47-33378 and JP-B-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, various additives such as stain inhibitors, sludge inhibitors, and multi-layer effect accelerators can be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify the starter and add the starter. As the starter, in addition to organic acids of polycarboxylic acid compounds, halides of alkaline earth metals such as KBr, organic inhibitors, and development accelerators are used.

The silver halide photographic light-sensitive material used in the present invention is not particularly limited, but the following are preferably used.

The emulsion used in the silver halide photographic light-sensitive material used in the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (197
December 8th) ・ Pages 22-23 1. Emulsion preparation
ration and types) and the same (RD) No. 18716 (November 1979)
-It can be prepared by the method described on page 648. Also,
For example, TH James “The theory of the photograp
hic process ”4th edition, published by Macmillan (1977) 38-104
GF Daufin "Photoemulsion Chemistry""Pho
tographic emulsion Chemistry ”, published by Focal press (19
66), P. Glafkides, "Physics and Chemistry in Photography," Chimie et
physique photographique ”published by Paul Montel (1967
), VL Zelikman et al., "Manufacturing and Coating of Photographic Emulsions""Ma
king and Coating Photographic Emulsion ”Focal pres
It is prepared by the method described in, for example, s company publication (1964).

The silver halide emulsions preferably used are, for example, JP-A-59-177535, 61-802237 and 61.
-132943, 63-49751 and JP-A-63-238225, and internal high iodine type monodisperse particles can be mentioned.
The crystal habit may be a cube, a tetradecahedron, an octahedron, and an intermediate (111) face and (100) face in any mixture. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. A preferred embodiment of the emulsion is a core / shell type monodisperse emulsion having a two-layer structure comprising a high iodine core portion and a low iodine shell layer.
The silver iodide content in the high iodine portion is 20 to 40 mol% and particularly preferably
20 to 30 mol%. Examples of these include J. Ph
ot.Sic.12.242-251 (1963), JP-A-48-36890, 52
-16364, 55-142329, 58-49938, British Patent 1,4
13,748, U.S. Patents 3,574,628, 3,655,394, British Patent 1,027,146, U.S. Patents 3,505,068, 4,444,877.
And JP-A-60-14331.

Another silver halide emulsion preferably used in the present invention is a tabular grain having an average aspect ratio of more than 1. The advantage of such tabular grains is that spectral sensitization efficiency can be improved, image graininess and sharpness can be improved, for example, British Patent 2,112,157 and U.S. Pat.
39,520, 4,433,048, 4,414,310, 4,434,22
6, JP-A-58-113927, 58-127921, 63-138342
No. 63-284272, No. 63-305343, etc., and the emulsion can be prepared by the method described in these publications.

In particular, Japanese Patent Application No. 4-289002 (pages 1 to 3), JP-A-59
-177535 (pages 2 to 5), Japanese Patent Application No. 4-277369 (pages 5 to 6) and JP-A-62-42146 (14 to 15) are preferably used.

Still another preferred silver halide emulsion used in the present invention is silver chlorobromide or silver chloride having a silver chloride content of 50% or more.

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. In these emulsions, a cadmium salt, a lead salt, a zinc acid, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, or the like may be used in the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or G3, G8 as an aggregation polymer agent described in JP-A-63-158644, etc. The method used is mentioned as a preferable desalting method. The chemical ripening method of the emulsion used in the light-sensitive material of the present invention is preferably gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, or a combination thereof.

In the emulsion of the light-sensitive material used in the present invention, various photographic additives can be used in the steps of physical ripening or chemical ripening. It is also possible to add a hydrazine compound, preferably the compound of Japanese Patent Application No. 5-134743,
In particular, the general formula (5) and the general formula (7) as a nucleation accelerator are
The compound of (8) is preferred. A tetrazolium salt may be added, and those described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure No. 17643 (December 1978), No. 1
8716 (November 1979) and 308119 (December 1989). The following table lists the types of compounds and the locations where they are described in these three Research Disclosures.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 966-8 IV Desensitizing dye 23 IV 998 B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26 to 7 XI 650 Right 1005 to 6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1003 to 4 IX Support 28 XVII Supports usable in the light-sensitive material of the present invention include, for example, RD17643, page 28 and RD-308119, 1009.
The thing described in the page is mentioned.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

Emulsion layers may be present on both sides of the support,
It may be on only one side. In the case of both sides, both sides may have the same performance or different performances.

[0136]

【Example】

Example 1 (1) Preparation of silver halide photographic light sensitive material <Preparation of emulsion> Silver iodide 1.3 mol% and the remaining 98.7 mol%
A silver iodobromide emulsion consisting of silver bromide was prepared. This emulsion had an average grain size of 1.22 μm, an average grain thickness of 0.41 μm and a grain size dispersibility of 0.23 according to the method described in JP-A-60-162244. The obtained emulsion was designated as (A).

Similarly, 1.3 mol% of silver iodide and the remaining 98.7%
A silver iodobromide emulsion having a mol% of silver bromide was prepared, and an emulsion having an average grain size of 0.69 μm, an average grain size thickness of 0.24 μm and a grain size dispersibility of 0.26 was obtained. And

Further, a silver iodobromide emulsion containing 1.4 mol% of silver iodide and the remaining 98.6 mol% of silver bromide was prepared. This emulsion was an octahedron having an average grain size of 0.58 μm, and the dispersibility of grain size was 0.17 in terms of variation coefficient. The obtained emulsion was designated as (C).

<Preparation of sample> The obtained emulsion (A),
The following sensitizing dyes (X) and (Y) were added to (B) and (C) at 55 ° C. in a weight ratio of 20: 1 to 400 mg per (A) and (B) per mol of silver halide. 900mg, 1100 for (C)
mg was added.

Sensitizing dye (X); 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl), oxacarbocyanine-sodium salt anhydride Sensitizing dye (Y ); 5,5'-di- (butoxycarbonyl), 1,
1'-Diethyl-3,3'-di- (4-sulfobutyl), benzimidazolocarbocyanine-sodium salt anhydride 10 minutes later, add an appropriate amount of chloroauric acid, sodium thiosulfate, ammonium thiocyanate Chemically aged. 40 minutes before the end of ripening, a 0.06 μm silver iodide fine grain emulsion was added at 6 × 10 ^−4.
Mol / Ag mol, then 4-hydroxy-6-methyl 1,
3,3a, 7-Tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide and dispersed in an aqueous solution containing 70 g of gelatin.

Thereafter, the emulsions (A), (B) and (C) were mixed at a molar ratio of silver halide of 10:65:25.

For this emulsion, JP-A-2-301744, page 95
Additives as shown on lines 16 to 96, line 20, were added.

Further, 1.0 g of the following dye emulsion dispersion was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresylphosphite and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent.

Next, an oil-based solvent and a water-based solvent were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C.

[0146]

Embedded image

The additives used in the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polymethylmethacrylate (matting agent having an area average particle size of 6.0 μm) 1.1 g Silicon dioxide particles (matting agent having an area average particle size of 3.0 μm) 0.5 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0149]

Embedded image

A 175 μm thick polyethylene terephthalate support colored blue with a support concentration of 0.15 was coated with a coating solution prepared so that the coating amount per one side would be the following composition, to form an undercoat layer.

Dye (exemplified compound below) 30 mg / m ² gelatin 0.7 g / m ² nonylphenoxy polyethylene oxide (polymerization degree = 10) 6 mg / m ² 1-morpholinocarbonyl-3- (pyridinio) methanesulfonate 80 mg / m ² poly Methyl methacrylate (matting agent with an average particle size of 2.5 μm) 2 mg / m ²

[0152]

Embedded image

On the undercoated support, the emulsion coating solution was 1.9 g / m ^{2 in} terms of silver per side, the amount with gelatin was 2.0 g / m ² , and the amount with gelatin in the protective layer was 0.9 g / m 2. ²
Thus, the emulsion layer and the surface protective layer were simultaneously extruded and coated at a speed of 90 m / min by a coating method, and dried for 2 minutes and 30 seconds to produce a silver halide photographic light-sensitive material.

A solid developer was prepared according to the following procedure (A, B).

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder,
After adding 3000 g of sodium sulfite, 2500 g of potassium sulfite and 1000 g of dimezone S for 30 minutes in a mill and granulating by adding 30 ml of water in a commercial stirring granulator at room temperature for about 10 minutes, Granules in a fluid bed dryer at 40 ° C for 2
The granules are dried for an hour to almost completely remove water. In this way, polyethylene glycol was added to the adjusted granules.
After uniformly mixing 100 g of 6000 with a mixer for 10 minutes in a room where the humidity was controlled to 25 ° C. and 40% RH or less, the resulting mixture was converted into a tough pressed collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The tablet was compressed with a tableting machine so that the filling amount per tablet was 3.84 g, and 2500 tablets A for development were prepared.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N
10 g of -acetyl-D, L-penicillamine is crushed and granulated in the same manner as in the operation (A). The amount of water added is 30.0 ml, and after granulation, 50 ℃
Dry for 30 minutes to remove almost completely the water content of the granulated product.
The mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 1.73 g per tablet to give 2500 developing tablets B. The agent was created.

Next, the solid fixing agent of the present invention was prepared by the following operations.

Procedure (C) 14000 g of ammonium thiosulfate / sodium thiosulfate (70/30 weight ratio) and 1500 g of sodium sulfite were pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Then, in the same manner as in (A), the amount of water added is set to 500 ml and granulation is performed. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product. In this way, the adjusted granules
Add N-lauroylalanine sodium 4g, 25 ℃,
Mix for 3 minutes with a mixer in a room conditioned to 40% RH or less. Next, the mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., so that the filling amount per tablet was 6.202 g, and 2500 fixing tablets C were prepared. Created.

Procedure (D) 1000 g of boric acid, 1700 g of Exemplified Compound (a-1), 3000 g of sodium hydrogen acetate (dried by mixing equimolar amounts of glacial acetic acid and sodium acetate), and 200 g of tartaric acid were pulverized in the same manner as in the procedure (A). , Granulate. Add water to 100 ml and after granulation, 50 ℃
Dry for 30 minutes to remove almost completely the water content of the granulated product.
In this way, 4 g of sodium N-lauroylalanine was added to the thus prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was manufactured by Kikusui Seisakusho Co., Ltd. Tough Pressed Collect 1527HU.
Filling amount per tablet is 4.719g by the tablet machine modified from
Then, compression tableting was carried out to prepare 1250 fixing supplement tablets D.

Operation (E) In the preparation of the solid fixing agent D, the exemplified compound (a-
1810 g of Exemplified Compound (a-2) was added instead of 1),
Fixing tablet E was prepared with a filling amount of 4.745 g per tablet.

Preparation of Comparative Solid Fixing Agent In the preparation of the solid fixing agent D, 1500 g of aluminum sulfate · 18-hydrate was added in place of the exemplified compound (a-1),
Fixing tablet F was prepared by setting the filling amount per tablet to 4.562 g.

The developing solution in the tank at the start was prepared to 1 liter by diluting 25 tablets each of the developing tablets A and B with diluting water. The following starter was added to 16.5 l of the developing solution prepared in this ratio, and the developing tank was filled as a starting solution to start the processing. As the fixing solution, CFL-881 (manufactured by Konica) was used as a starting solution.

Developer Starter The pH of the developer containing the glacial acetic acid 2.98 g KBr 4.0 g starter was 10.45.

The light-sensitive material prepared above was cut into a large square size, uniformly exposed to light so that the optical density after development was 1.0, and running was carried out. During the running, the developer was prepared by adding 2 each of the above-mentioned agents A and B and 38 ml of water per 0.15 m ² of the light-sensitive material. The pH was 10.70 when two of each of A and B were dissolved in 38 ml. To the fixing solution were added 2 parts of the above-mentioned C agent, 1 part of D agent, E agent or F agent and 37 ml of water per 0.15 m ² of the light-sensitive material. The pH when the two C agents and one D agent were dissolved in 37 ml of water was 4.30.

The automatic processing machine was processed using the following materials.

Automating machine 1: SRX-502 (manufactured by Konica) was equipped with a solid processing agent input section, and the processing speed (DRY TO DRY) was 25.
Remodeled so that it can be processed in seconds Developed machine 2: SRX-503 (manufactured by Konica) was equipped with a solid processing agent input section, and was remodeled so that processing speed (DRY TO DRY) could be processed in 25 seconds. The temperature of the infrared heater was 220 ° C. The automatic processing machine 3: SRX-502 (manufactured by Konica Corporation) was equipped with a solid processing agent injection section and was modified so that the processing speed (DRY TO DRY) could be processed in 25 seconds. The roller in the drying process was modified so that the surface temperature was 90 ° C. The developing temperature during running was 35 ° C and the fixing temperature was 33 ° C.
The warm air of the drying fan was set to 55 ° C.

The running time was 25 seconds, 45 seconds, and 90 seconds, respectively.

(Evaluation of Drying Property) The sample used for running was touched with the film immediately after being discharged from the discharge port through the drying section of the automatic developing machine, and the touch was evaluated according to the following evaluation criteria.

Evaluation Criteria 5: The film is completely dry and the whole film is warm.

4: Completely dry, but part of the film is cold.

3: The film is dry and has no problem in practical use, but the entire film is cold.

2: Part of the edge of the film is wet.

1: The whole sample is wet.

(Evaluation of drying unevenness) For a large-angle sample,
The entire surface was exposed uniformly so that the optical density after development was 1.0, and the same development treatment as in the above sensitometry was performed. The developed sample was observed on Schaukasten, and the degree of occurrence of drying unevenness was visually evaluated. The evaluation criteria are as follows.

A: No occurrence is observed B: Some occurrence but no problem in practical use C: Many occurrences D: Occurrence on the entire surface Table 1 shows the evaluation results.

The evaluation of the drying property and the evaluation of the drying unevenness were made when the sample insertion interval to the developing machine during running was 10 minutes, and the sample insertion interval was further shortened to 30 seconds and 10 seconds, respectively. I did about running. As the evaluation sample of drying property and drying unevenness, the 500th sample was used for each running.

[0177]

[Table 1]

As is clear from Table 1, the solid fixing agent using the aluminum complex of the present invention can obtain good drying property even in continuous treatment with a short treatment interval. It can be seen that the fixing agent is sufficiently dissolved. This is especially noticeable in dry processing of 30 seconds or less. Further, with the conventionally known fixing agent using aluminum sulfate, the dissolution time was insufficient in a short continuous treatment, sufficient drying property was not obtained, and uneven drying occurred.

[0179]

According to the present invention, the solid fixing agent is sufficiently dissolved even in continuous processing with a short processing interval, and good drying property is obtained. In particular, a remarkable effect can be seen in the rapid processing of Dry To Dry for 30 seconds or less.

In the drying step, infrared radiation drying or an automatic developing machine equipped with a heat roller can be used to perform good processing without drying unevenness.

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Claims (5)

[Claims] 1. A fixing agent for a silver halide photographic light-sensitive material, wherein the fixing agent is a solid fixing agent and contains aluminum ions in the form of a complex. Agent. 2. A method for continuously processing a silver halide photographic light-sensitive material in a development processing apparatus including a developing tank filled with a developing solution and a fixing tank filled with a fixing solution, wherein a solid fixing agent containing an aluminum complex is fixed as described above. A method for processing a silver halide photographic light-sensitive material, which comprises directly replenishing and adding to a tank or a fixing replenishing tank for introducing a processing liquid from the fixing tank in accordance with the amount of silver halide photographic light-sensitive material to be processed. 3. The processing of a silver halide photographic light-sensitive material according to claim 2, wherein the time from the start of immersion of the silver halide photographic light-sensitive material in a developing solution to the end of drying is 30 seconds or less. Method. 4. The method of processing a silver halide photographic light-sensitive material according to claim 2, wherein the silver halide photographic light-sensitive material is processed by an automatic processor that uses infrared radiation drying in the drying step. . 5. The processing of the silver halide photographic light-sensitive material according to claim 2 or 3, wherein the silver halide photographic light-sensitive material is processed by an automatic processor equipped with a heat roller in the drying step. Method.