JP2950479B2 - Automatic development processing apparatus and processing method - Google Patents

Description

The present invention relates to an automatic developing apparatus and a processing method for a black-and-white silver halide photographic light-sensitive material. In addition, clogging of pipes due to precipitation in the fixing solution and contamination of photographic photosensitive materials,
The present invention also relates to an automatic developing apparatus and a processing method for a black-and-white silver halide photographic light-sensitive material free from poor drying due to insufficient hardening.

[Conventional technology]

Conventionally, after developing a silver halide photographic material, a fixing solution containing thiosulfate (thiosulfate ion) as a fixing agent, which gives the best water-soluble complex of silver halide,
Further, it is known that a fixing treatment with a sulfite-containing fixing solution is carried out in order to prevent oxidative decomposition of thiosulfate and to efficiently elute a water-soluble complex ion of silver halide and thiosulfate ion from a binder of a photosensitive material. ing.

It is also known that aluminum ions and the like are contained in a fixing solution to improve the drying property in drying after the fixing process.

[Problems to be solved by the invention]

In recent years, awareness of environmental issues has been raised, and a fixing solution free of odor due to sulfurous acid gas, ammonia gas, and the like generated from a fixing solution of an automatic developing machine has been desired. In addition, the use of highly electronic and precision-mechanized equipment has become popular, and corrosion of equipment due to sulfurous acid gas generated from a fixing solution of an automatic developing machine has become a problem. Needless to say, there is a demand for shortening the processing time of the photosensitive material.

Usually, the fixing solution is set at pH 5 or less. The generation of sulfurous acid gas and volatile acids can be improved by increasing the pH of the fixing solution. However, when this pH is increased, aluminum hydroxide precipitates. Further, when the developing speed of the developing agent contained in the developing solution depends on the pH and the pH of the fixing solution rises, so-called physical development occurs, and there is a problem that blackened silver is generated even in the unexposed area.

Accordingly, the present invention provides a black-and-white silver halide which is free from odor generation and metal corrosion caused by sulfurous acid gas, and free from drying clogging due to clogging of pipes due to precipitation in a fixing solution and insufficient stiffness of a photographic material. It is an object of the present invention to provide an automatic developing apparatus and a processing method for a photographic photosensitive material.

[Means for solving the problem]

An object of the present invention is to provide a first processing tank for reducing a silver halide of an image-exposed black-and-white silver halide photographic light-sensitive material to form a silver image, and a halogenation remaining in the light-sensitive material after processing in the first processing tank. A second processing tank for fixing and removing silver, a third processing tank for performing a cleaning process after the fixing process in the second processing tank, and a drying unit for drying the photosensitive material after the cleaning process in the third processing tank Wherein the fixing processing liquid supplied to the second processing tank is a fixing processing liquid containing thiosulfate and sulfite and having a pH of 6 or more, wherein the first processing tank and the Having a means for bringing the photosensitive material into contact with an aqueous solution of an acidic organic substance having an acidic group and being substantially non-volatile between the second processing tank; In between, the photosensitive material and an aqueous solution containing an organic hardener Having means brought into contact is achieved by the treatment method using an automatic developing apparatus and an apparatus for black-and-white silver halide photographic light-sensitive material characterized.

In a preferred embodiment of the present invention, the thiosulfate concentration in the fixing solution is 0.01 mol / or more, the sulfite concentration in the fixing solution is 0.01 mol / or more,
-9.

 Hereinafter, the present invention will be described in detail.

The automatic developing apparatus of the present invention will be described with reference to FIG.

In FIG. 1, reference numeral 1 denotes a first processing tank, that is, a developing processing tank, in which a silver halide of an image-exposed black-and-white silver halide photographic light-sensitive material F is reduced to form a silver image. Reference numeral 2 denotes a second processing tank for fixing and removing silver halide remaining in the photosensitive material F after processing in the first processing tank (development processing tank) 1, that is, a fixing processing tank. Reference numeral 3 denotes a third processing tank for performing cleaning processing after the fixing processing in the second processing tank (fixing processing tank), that is, a cleaning processing tank. Reference numeral 4 denotes a drying unit for drying the photosensitive material F after the cleaning processing in the third processing tank (cleaning processing tank) 3.

Means for bringing the photosensitive material F into contact with a specific aqueous solution of an acidic organic substance is provided, for example, at a transition portion between the first processing tank 1 and the second processing tank 2. The contacting means may be any means as long as it allows the aqueous solution of the acidic organic substance to reach at least a part of at least one surface of the photographic material.

As a specific example, a method of providing a new processing tank containing the acidic organic substance aqueous solution according to the present invention between the first processing tank and the second processing tank, and immersing the photosensitive material transported from the first processing tank A method in which a roller is provided between the first processing tank and the second processing tank, and the acidic organic substance aqueous solution according to the present invention is supplied to the surface of the roller by adhesion or swelling, and the roller is brought into contact with the photosensitive material. A method of spraying the acidic organic substance aqueous solution according to the present invention, a method of bringing the aqueous solution into contact with a jet liquid flow or a curtain liquid flow, and a method of forming a liquid pool of the aqueous solution between the photosensitive material and the wall material. Can be

FIG. 1 shows an example in which an acid treatment means 5 is provided as an example of such a contact means. Reference numeral 51 denotes a semi-cylindrical guide plate provided at a transition portion between the first processing tank 1 and the second processing tank 2 so as to regulate the upper part of the conveying path of the photosensitive material F. Reference numeral 52 denotes a treatment tank provided below the guide plate 51 and containing an aqueous acidic organic substance solution. A first roller 53 is provided on the upper part of the processing tank 52 to be in contact with the acidic organic substance aqueous solution. A second roller 54 is provided so as to be in contact with the first roller 53, and further is in contact with the second roller 54. Like transport roller
55 (which may be guide rollers) are provided.
For this reason, via the first roller 53 and the second roller 54,
That is, the acidic organic substance aqueous solution is moved to the transport roller 55 by the adhesion or swelling action. Therefore, the aqueous solution can be supplied to the photosensitive material F in contact with the transport roller 55.

In FIG. 1, reference numeral 56 denotes a blade for scraping off the acidic organic substance aqueous solution. The scraped aqueous solution is returned to the first roller 53, the second roller 54, the transport roller 55, or the processing tank 52. Is also good.

Means for bringing the photosensitive material F into contact with an aqueous solution containing an organic hardener is provided between the third processing tank 3 and the drying unit 4, for example, in the transition unit. The contacting means may be any means as long as it allows the aqueous solution containing the organic hardener to reach at least a part of at least one surface of the photosensitive material.

As a specific example, a new processing tank containing the aqueous solution containing the organic hardener according to the present invention is provided between the third processing tank and the drying unit, and the photographic photosensitive material transported from the first processing tank is immersed. A method in which a roller is provided between the third processing tank and the drying section, and the organic hardener-containing aqueous solution according to the present invention is supplied to the surface of the roller by adhesion or swelling, and the roller is brought into contact with the photosensitive material. A method of spraying an aqueous solution containing an organic hardener according to the present invention, a method of bringing the aqueous solution into contact with a jet liquid stream or a curtain liquid stream, and forming a pool of the aqueous solution between a photosensitive material and a wall material. Method, etc.

FIG. 1 shows an example in which an organic hardener treatment means 6 is provided as an example of such a contact means. Reference numeral 61 denotes a treatment tank provided in the transition section and containing an aqueous solution containing an organic hardener. A first roller 62 in contact with the aqueous solution containing the organic hardener is provided above the processing tank 61, and a transport roller 63 is provided in contact with the first roller 62. Therefore, the organic hardener-containing aqueous solution is moved to the transport roller 63 via the first roller 62, that is, due to the adhesion or swelling action. Therefore, the aqueous solution can be supplied to the photosensitive material F in contact with the transport roller 63.

The drying means that can be employed in the drying unit 4 according to the present invention may be any method as long as it is a means for drying the wet photographic material transported from the third processing tank. Specific examples include a method using heated air, a method using dehumidified air, a method of applying microwaves to a photographic material, a method of contacting a photographic material with a heated roller, and a method of applying far-infrared rays to a photographic material. Irradiation method and the like can be mentioned.

Hereinafter, a processing method using the automatic developing apparatus of the present invention will be described.

The fixing solution used in the processing apparatus of the present invention contains a thiosulfate and a sulfite.

The thiosulfate is not particularly limited as long as it can dissociate thiosulfate ions into the fixing solution. Preferably, thiosulfate ions and alkali metal cations, or quaternary aminium cations to which amines are protonated, are used. can give. Particularly preferably, sodium ion or 1,5-Diazabicyclo [4,3,0] non-5-ene, 1,8-Diazabicyclo [5,4,0] -7-undecene, and 1,4-Diazabicyclo [ 2,2,2] octane protonated cations.

The addition amount of the thiosulfate is preferably 0.01 mol / or more, more preferably 0.5 to 2 mol /, further preferably 0.7 to 1.8 mol /.

As the sulfite, any substance may be used as long as the substance dissociates the sulfite ion into the fixing solution, but preferably a sulfite ion, an alkali metal cation, and a quaternary aminium cation in which an amine is protonated. Particularly preferably, sodium ion or 1,5-Diazabicyclo [4,3,0] non-5-ene, 1,8-Diazabicyclo [5,4,0] -7-undecene, and 1,4-Diazabicyclo [ 2,2,2] octane protonated cations.

The sulfite concentration in the fixing solution is preferably at least 0.01 mol /, more preferably in the range of 0.01 to 1 mol /.

The pH of the fixing solution may be 6 or more, and preferably 7 to
9 is in the range.

The fixing processing time is preferably 30 seconds or less, and the processing temperature is
25 ° C to 42 ° C is preferred.

For the fixer, citric acid, isocitric acid, malic acid, succinic acid and salts thereof can be used.
Potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, ammonium tartrate, ammonium potassium tartrate, sodium potassium tartrate, Lithium, potassium, sodium represented by sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc.
Ammonium salts and the like.

In addition, the fixing solution may contain additives such as various acids, salts, chelating agents, surfactants, wetting agents, and fixing accelerators, in addition to the compounds described above. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid and oxalic 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 surfactant include an anionic surfactant such as a sulfonate, a nonionic surfactant such as a polyethylene glycol or an ester, and an amphoteric surfactant described in JP-A-57-6840. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include, for example, JP-B-45-35754 and 58-122535.
And thiourea derivatives described in U.S. Pat. No. 4,126,459. The fixing agent may further contain a hardening agent.

In the present invention, particularly preferred examples of the acidic group in the `` acidic organic substance having an acidic group and being substantially non-volatile '' used for the contact means provided between the first processing tank and the second processing tank include: Examples include a carboxy group, a sulfonic acid group, a sulfinic acid group, and a phosphoric acid group. The term “substantially non-volatile” means that the weight loss is 0.1% or less even when left open for 500 hours under an environment condition of 34 ° C./20% RH. Particularly preferred specific examples of the acidic organic substance include citric acid, tartaric acid, malic acid, succinic acid, p-toluenesulfonic acid, p-toluenesulfinic acid, and methylphosphoric acid.

In the present invention, the organic hardening agent used in the contact means provided between the third processing tank and the drying section includes an organic substance which reacts with a main binder of a silver halide emulsion layer of a silver halide photographic light-sensitive material and is cured. Any compound may be used.

As the hardening agent used in the present invention, aldehyde-based hardening agents,
Aziridine-based (eg, PB Report, 19,921, US Patent
2,950,197, 2,964,404, 2,983,611, 3,27
No. 1,175, JP-B-46-40898, JP-A-50-91315), isoxazoles (for example, US Pat.
No. 609), epoxy type (for example, US Pat.
47,394, West German Patent 1,085,663, British Patent 1,033,518
No., JP-B-48-35495), vinyl sulfone type (for example, PB Report 19,920, West German Patent 1,100,94)
No. 2, No. 2,337,412, No. 2,545,722, No. 2,635,518,
No. 2,742,308, No. 2,749,260, UK Patent 1,251,091
No., Japanese Patent Application Nos. 45-54236, 48-110996, U.S. Pat.
39,644 and 3,490,911), acryloyl-based (for example, Japanese Patent Application No. 48-27949, U.S. Pat. No. 3,640,720)
Carbodiimides (for example, those described in U.S. Pat. Nos. 2,938,892, 4,043,818, 4,061,499, JP-B-46-38715, and JP-A-49-15095), triazines (for example, West German Patent 2,410,973, 2,553,9
No. 15, U.S. Pat.No. 3,325,287, those described in JP-A-52-12722), polymer type (for example, U.S. Pat.No. 822,061, U.S. Pat.No. 3,623,878, 3,396,029, 3,226,234,
JP-B-47-18578, JP-B-47-18579, JP-B-47-48896), and other maleimide-based, acetylene-based, methanesulfonic acid ester-based (N-methylol-based) hardeners alone or Can be used in combination. As useful combination techniques, for example, West German Patent Nos. 2,447,587 and 2,50
5,746, 2,514,245, U.S. Pat.Nos. 4,047,957, 3,8
32,181, 3,840,370, JP-A-48-43319, 50-
63062, 52-127329, and JP-B-48-32364.

In the present invention, the concentration of the organic hardener is preferably 10 ^-6 mol / or less.

In the present invention, development with a developing solution is performed before processing with a fixing solution. The developer is preferably a solution containing the following developing agents.

That is, as a black-and-white developing agent, dihydroxybenzenes (for example, hydroquinone, chlorohydroxone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, and 3-pyrazolidones (for example, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-dimethyl-
3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 , 4-dihydroxymethyl-3-pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4- 1-aryl-3-aminopyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3)
-Aminopyrazoline, etc.) and mixtures thereof.

These developing agents are preferably usually 0.1 to 80 g /,
More preferably, it is used at a concentration of about 0.2 to 50 g /.

If necessary, the developing solution may contain a preservative (eg, sulfurous acid, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine, etc.), an alkaline agent (eg, hydroxide, carbonate, etc.) ), Dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as acetic acid), sensitizers (eg, quaternary ammonium salts), development accelerators, hardening Agents (eg, dialdecans such as glutaraldehyde), surfactants, and the like. The developer may further contain an antifoggant (for example, a halide such as potassium bromide or sodium bromide, benzotriazole,
Benzothiazole, tetrazole, thiazole, etc.),
Chelating agents (eg, ethylenediaminetetraacetic acid, alkali metals thereof, polyphosphoric acid hydrochloride, nitriloacetate, etc.)
Can be contained.

The silver halide photographic light-sensitive material to which the present invention can be applied may be any one having a support and a photographic component layer including at least one silver halide emulsion layer formed thereon.
Further, the silver halide emulsion layer may be coated not only on one side of the support but also on both sides. Further, the photographic constituent layer may include a backing layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer) and the like.

Silver halide emulsions, for example, silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, hydrophilic colloids such as gelatin, modified gelatin,
Colloidal albumin, casein, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone,
It is dispersed in an acrylate, a methacrylate or a mixture thereof.

Silver halide emulsions are generally prepared by methods well known in the art (eg, single jet method), double jet method,
A water-soluble silver salt (eg, silver nitrate) and a water-soluble halogen salt are mixed in the presence of water and a hydrophilic colloid by a control jet method or the like, and subjected to physical ripening and chemical ripening such as gold sensitization and / or sulfur sensitization. It is manufactured through

Emulsions thus obtained include cubic, octahedral,
In addition to the spherical shape, Research Disclosure (Research D
isclosure) 22534 (January 1953), tabular silver halide grains having a high aspect ratio can be used, and the internal latent image type silver halide grains described in JP-B-41-2065 can be used. It can be used in combination with a surface latent image type silver halide grain.

During the production process or immediately before coating, the silver halide emulsion has a spectral sensitizer (for example, a cyanine dye, a melonia cyanine dye or a mixture thereof), a stabilizer (for example,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene), sensitizers (for example, compounds described in U.S. Pat. No. 3,619,198), antifoggants (for example, 5-nitrobenzimidazole and the like) Benzotriazoles, polyethylene oxide), hardeners (eg, formalin, glyoxal, mucochloric acid, 2-hydroxy-4,6-dichloro-s-triazine), coating aids (eg, saponin, sodium lauryl sulfate, dodecylphenol) Polyethylene oxide ether, hexadecyltrimethylammonium bromide) and the like can be added.

The silver halide emulsion thus produced is applied to a support such as baryta paper, resin coated paper, cellulose acetate film, polyethylene terephthalate film, etc. by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-side coating method, etc. Is applied and dried.

An antistatic layer containing a water-soluble conductive polymer, a hydrophobic polymer, a hardener, a surfactant and the like can be formed on the support.

Examples of the black-and-white silver halide photographic material to which the present invention is applied include, for example, medical or industrial X-ray photographic materials,
There are a photographic material for photoengraving, a micro photographic material, a micro-inverted photographic material for X-ray, a paper photographic material for computer printing, a negative photographic material for general photography, and photographic paper.

Preferred silver coating amount of silver halide photographic light-sensitive material to which the present invention is applied is 1 to 25 g / m ^2, more preferably 1.
It is 5 to 12 g / m ² , most preferably 2.0 to 6 g / m ² .

Preferred coating weight of the hydrophilic colloid of the silver halide photographic light-sensitive material to which the present invention is applied is a single-sided per 1 to 5 g / m ² of the support, more preferably fit both sides of the support 1.5~4.5g / m ² , and the most preferable coating amount of the hydrophilic colloid is 1.5 to 3.5 g / m ² on both sides of the support.

A preferred black-and-white silver halide photographic light-sensitive material is a light-sensitive material for photoengraving and is suitable because the swelling of the film surface is not large. Most preferably, JP-B Nos. 52-18317 and 53-9
Nos. 5618, 58-173737 and 58-106493, as described in JP-A-61-223734.
A photoengraving photosensitive material containing a hydrazine derivative as described in JP-A-61-223834.

〔Example〕

Hereinafter, the present invention will be further described with reference to Examples. Needless to say, the present invention is not limited by the embodiments.

[Preparation of fixing solutions 1 to 3] Sodium thiosulfate 200 g Sodium sulfite 17 g Boric acid 7 g Sodium sulfate 24 g Sodium citrate 2 g After adding pure water to the above material and dissolving, pure water and citric acid were added to set the pH shown in Table 1 below. Alternatively, finishing was performed while adding sodium hydroxide to 1 to prepare Fixing Solutions 1 to 3 shown in Table 1 below.

[Preparation of fixers 4 to 6] Sodium thiosulfate 200 g Sodium sulfite 17 g 27% aqueous solution of aluminum sulfate 34 g Boric acid 7 g Sodium sulfate 24 g Sodium citrate 2 g Sodium rhodanate 30 g The pH was adjusted to 1 while adding pure water and acetic acid or sodium hydroxide to 1 to prepare fixers 4 to 6 shown in Table 1 below.

[Preparation of Organic Hardener-Containing Treatment Solution] A 2% aqueous solution of the organic hardener shown in Table 1 below was prepared by adding pure water.

[Automatic Developing Apparatus] No. 1: Automatic developing apparatus of the present invention shown in FIG. 1 No. 2: Comparison of the apparatus shown in FIG. 1 except that acid processing means 5 and organic hardener processing means 6 were removed [Preparation of light-sensitive material for printing for evaluation] A negative-type silver halide light-sensitive material was prepared as a light-sensitive material for returning light in the following manner.

(Preparation of Emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

While stirring an aqueous solution containing 23.9 mg of pentabromorhodium potassium salt, sodium chloride and potassium bromide and an aqueous solution of silver nitrate per 60 g of silver nitrate in an aqueous gelatin solution,
Simultaneous mixing was performed at 40 ° C. for 25 minutes to prepare silver chlorobromide emulsions having an average particle size of 0.20 μm.

200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added to this emulsion as a stabilizer, followed by washing with water and desalting.

20 mg of 6-methyl-4-hydroxy-1,3,3a, 7
Sulfur sensitization after the addition of tetrazaindene. After sulfur sensitization, add the necessary amount of gelatin, add 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer, and finish with 260 ml of water to prepare an emulsion. did.

(Preparation of latex (L) for adding emulsion) 0.25 kg of KMDS (dextran sulfate sodium salt) and 0.05 kg of ammonium persulfate in water 40
A liquid mixture of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added over 1 hour to the added liquid while stirring at a liquid temperature of 81 ° C. under a nitrogen atmosphere, and then 0.005 kg of ammonium persulfate was added. After stirring for 1.5 hours, cooling,
Further, the pH was adjusted to 6 with aqueous ammonia.

The obtained latex liquid was filtered off with a GF / D filter manufactured by Whotman, and finished with water to 50.5 kg to prepare a monodisperse latex (L) having an average particle size of 0.25 μm.

The following additives were added to the emulsion to prepare a silver halide emulsion coating solution as described below.

(Preparation of Emulsion Coating Solution) After adding 9 mg of the compound (A) as a bactericide to the emulsion solution, the pH was adjusted to 6.5 using 0.5 N sodium hydroxide solution, and then 360 mg of the following compound (T) was added. 5 mol of a 20% aqueous solution of saponin per mol of silver halide, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, 43 ml of the latex solution (L) for adding an emulsion were added, and the following compound (M) was added. An emulsion coating solution was prepared by sequentially adding 60 mg and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener and finishing with 475 ml with water.

 Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of emulsion protective film coating solution) Pure water was added to 50 g of gelatin, and after swelling, dissolved at 40 ° C. Then, as a coating aid, 30.5 ml of a 4% aqueous solution of the following compound (Z) was used. 6.7 g of the compound (N) and 30.9 ml of a 10% methanol solution of the following compound (D) were sequentially added, and the mixture was further adjusted to pH 5.5 with a citric acid solution. 0.9 g and 0.4 g of amorphous silica matting agents of SYLOD 74 and 266 manufactured by Fuji Devison Co., Ltd. having an average particle diameter of 6 μm were added, and 975 ml was finished with pure water to prepare a coating solution for an emulsion protective film.

Next, a backing coating solution used for coating the backing lower layer was prepared as follows.

(Preparation of Backing Coating Solution) 36 g of gelatin was swollen in water, heated and dissolved, and then 1.6 g of the following compound (C-1) and 310 m of (C-2) were used as dyes.
g, 1.9 g of (C-3), 2.9 g of the compound (N) in the form of an aqueous solution, and then 11 ml of a 20% aqueous solution of saponin, and 5 g of the following compound (C-4) as a physical property modifier were further added. As a methanol solution, 63 mg of the following compound (C-5) was added. As a thickener, 800 g of a water-soluble styrene-maleic acid copolymer was added as a thickener to adjust the viscosity, the pH was adjusted to 5.4 with an aqueous citric acid solution, 144 mg of glyoxal was further added, and an epoxy-based curing agent (H ) Was added to 2.0 g, and finished to 960 ml with water to prepare a BC coating solution.

Next, a protective film coating solution was prepared as follows for coating the protective film layer of the backing layer.

(Preparation of Coating Solution for Backing Layer Protective Film) Gelatin (50 g) was swollen in water and dissolved by heating. Then, 340 mg of 2-sulfonate-bis (2-ethylhexyl) succinate sodium salt was added, and 3.4 g of sodium chloride was added. 1.1 g of glyoxal and 540 mg of mucochloric acid
added. To this, spherical polymethyl methacrylate having an average particle size of 4 μm was added as a matting agent so as to have a concentration of 40 mg / m ^2, and finished to 1000 ml with water to prepare protective film coating solutions.

(Preparation of a support having an antistatic layer) 50 W / m ² ·
After a corona discharge with an energy of min, an antistatic solution having the following composition was applied using a roll-fit coating pan and an air knife at a speed of 30 m / min so as to give the following amount.

Water-soluble conductive polymer (A) 0.6 g / m ² Hydrophobic polymer particles (B) 0.3 g / m ² Hardener H 0.15 g / m ² Nonionic activator (C) 0.06 g / m ² After drying for 2 minutes and heat treatment at 140 ° C. for 90 seconds, a support having an antistatic layer was prepared.

[Preparation of photographic light-sensitive material] Using the above support, the backing layer coating solution and the backing layer protective film coating solution were used to adjust the gelatin weight of the backing layer to 2.5 g / m ² and the gelatin weight of the protective film layer to 2.5 g / m ^2. Co-application was carried out to 1.0 g / m ² .

Then the halide amount with silver 47 g / m ² of the emulsion layers with each emulsion layer coating solution on the opposite side on the support and the emulsion protective layer coating solution, also the amount with the gelatin protective layer of 1.0 g / m ² to obtain a photosensitive material. The drying conditions used at that time are shown below.

<Drying condition at the time of application> After applying the application liquid at 35 ° C, the coating liquid is treated with cold air at 5 ° C for 6 seconds,
Cooling and coagulation, and then using a dry air with a dry bulb temperature of 23 ° C and a relative humidity of 20% at a coating surface temperature of 10 ° C, the coating layer gelatin water content is 16
It was dried to 00% and then dried to a water content of 800% using a drying air at a drying temperature of 27 ° C. and a relative humidity of 20%. Next, drying was performed at a drying temperature of 34 ° C. so as to satisfy the drying condition A. After the average temperature of the coated and dried surface reached 33 ° C., the coating was dried under drying condition B after 5 seconds.

Drying condition A Dry for 30 seconds using a dry air having a dry bulb temperature of 34 ° C and a wet bulb temperature of 14 ° C.

Drying condition B Drying is performed for 30 seconds using a dry air having a dry bulb temperature of 48 ° C and a wet bulb temperature of 15 ° C.

[Preparation of developer for evaluation] (Composition A) Pure water (ion-exchanged water) 150 ml Disodium salt of ethylenediaminetetraacetic acid 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzo Triazole 200 ml 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to make the pH of the working solution 10.9 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg At the time of using a developer, the above composition A and composition B were dissolved in 500 ml of water in that order, and used after finishing to 1.

[Development processing conditions] Process temperature Time Developing 34 ° C 15 seconds Transfer or acid processing means Room temperature 2 seconds Fixing 34 ° C 15 seconds Transfer Room temperature 2 seconds Water washing Room temperature 10 seconds Transfer or organic hardener processing means Room temperature 2 seconds Drying 45 ° C 8 seconds [Evaluation Method] The above developer, the above two kinds of automatic developing apparatuses, and the above 3
The various types of fixing solutions were combined as shown in Table 1 below and operated under the above-mentioned processing conditions. The above-mentioned silver halide photographic light-sensitive material for evaluation was continuously processed, and the following evaluations were made.

(Evaluation of Odor) After driving for 1 hour, the lid at the top of the device was opened, and the odor was evaluated by sensory evaluation using a human nose. The evaluation rank is described below. The results are shown in Table 1.

Rank 1: Smelly smell Rank 2: Slight smell Rank 3: No smell at all (Evaluation of metal corrosion by fixer) 50ml of each fixer shown in Table 1 below is placed in a 200ml autoclave and the inside of the container lid With a commercially available iron nail attached with tape, seal the autoclave,
After keeping it at 34 ° C for 60 days, it was opened, the iron nail was taken out from the lid, and the occurrence of corrosion was observed. The results are shown in Table 1 below.

(Evaluation of physical development fog on unexposed area) The above photographic photosensitive material cut to 610 mm x 508 mm was unexposed.
Thirty sheets were continuously processed, and the fog silver concentration of the last processed one was measured.

(Evaluation of drying property) The above photographic photosensitive material cut to 610 mm x 508 mm was left unexposed.
Thirty sheets were continuously processed, and the degree of drying of the finally processed one was evaluated by touch feeling by hand. The results are shown in Table 1 below.

(Evaluation of Precipitate in Fixing Solution) After continuously operating for 30 days in each of the processing methods shown in Table 1, the automatic developing apparatus was stopped, and the presence or absence of a precipitate in the fixing processing tank was observed.

[Evaluation Results] As is clear from Table 1, Experiment N according to an embodiment of the present invention was performed.
No odors, no metal corrosion, no poor drying, only by the treatment methods of o.5 and 6, and No.13,14,15,
Further, it can be seen that there is no precipitation in the fixing solution and no unexposed fog silver is generated.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to this invention, there is no concern about generation of odor and metal corrosion due to sulfurous acid gas, and black-and-white halogenation without clogging of pipes due to precipitation in a fixing solution, and poor drying due to contamination of photographic light-sensitive materials and insufficient hardening. An automatic developing apparatus and a processing method for a silver photographic light-sensitive material can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of the automatic development processing apparatus of the present invention. DESCRIPTION OF SYMBOLS 1 ... 1st processing tank 2 ... 2nd processing tank 3 ... 3rd processing tank 4 ... Drying part 5 ... Acid processing means 6 ... Organic hardening agent processing means

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-67556 (JP, A) JP-A-62-139548 (JP, A) JP-A-1-193853 (JP, A) JP-A-2- 125249 (JP, A) JP-A-2-852 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03D 3/00-17/00

Claims (5)

(57) [Claims] 1. A first processing tank for reducing a silver halide of an image-exposed black-and-white silver halide photographic material to form a silver image, and a halogen remaining in the photographic material after processing in the first processing tank. A second processing tank for fixing and removing silver halide, a third processing tank for performing a cleaning treatment after the fixing processing in the second processing tank, and drying for drying the photosensitive material after the cleaning processing in the third processing tank. Wherein the fixing solution supplied to the second processing tank is a fixing solution having a pH of 6 or more containing thiosulfate and sulfite, and the first processing tank and the second Having a means for bringing the photosensitive material into contact with an aqueous solution of an acidic organic substance having an acidic group and being substantially non-volatile between the second processing tank; and between the third processing tank and the drying unit. Contact the photosensitive material with an aqueous solution containing an organic hardener. Have a Mel means, an automatic developing apparatus for black-and-white silver halide photographic light-sensitive material characterized. 2. A first processing tank for reducing a silver halide of an image-exposed black-and-white silver halide photographic light-sensitive material into a silver image, and halogen remaining in the light-sensitive material after processing in the first processing tank. A second processing tank for fixing and removing silver halide, a third processing tank for performing a cleaning treatment after the fixing processing in the second processing tank, and drying for drying the photosensitive material after the cleaning processing in the third processing tank. Wherein the fixing solution supplied to the second processing tank is a fixing solution having a pH of 6 or more containing thiosulfate and sulfite, wherein the first Having a means for bringing the photosensitive material into contact with an aqueous solution of an acidic organic substance having an acidic group and being substantially non-volatile between the processing tank and the second processing tank; Between the drying section, contains the photosensitive material and an organic hardener Having means brought into contact with a solution, the processing method of the black-and-white silver halide photographic light-sensitive material using an automatic developing apparatus according to claim. 3. The fixing solution having a thiosulfate concentration of 0.01 mol / mol.
A method for processing a black-and-white silver halide photographic material using the automatic development processor according to claim 2. 4. A method for processing a black-and-white silver halide photographic material using an automatic development processor according to claim 2, wherein the sulfite concentration in the fixer is 0.01 mol / or more. 5. A method for processing a black-and-white silver halide photographic material using an automatic developing apparatus according to claim 2, wherein the pH of the fixing solution is 7 to 9.