JP2832365B2 - Processing of silver halide black-and-white photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly, to a silver halide black-and-white photographic light-sensitive material having improved water saving efficiency and improved rapid processing performance. The present invention relates to a material processing method.

[Background of the Invention]

At present, development processing of a silver halide photosensitive material is generally performed using an automatic developing machine, but such an automatic developing machine usually includes development, fixing, washing, and drying steps. After the development and the fixing process, the photosensitive material, which is included in the material in the water washing step, is subjected to the washing process to remove the processing solution components in the previous step, particularly the fixing solution components. If the washing is insufficient, especially in a black-and-white silver halide photosensitive material, performance problems such as deterioration of an image with time due to a residual fixing solution component in the material occur. Therefore, it is necessary to perform sufficient rinsing to sufficiently remove the residual fixing solution components in the photosensitive material. However, as described above, sufficient rinsing cannot be performed with the amount of rinsing water contained in the rinsing tank in the automatic developing machine. Met. For this reason,
At present, tap water is always supplied at the time of rinsing treatment, and the overflowing rinsing water is drained to the sewer as it is at present.

Under the circumstances as described above, in recent years, from the viewpoint of resource saving and reduction of production cost, the demand for water saving at the time of washing of the automatic developing machine has been increasing, and the demand for technical improvement accompanying this has been increasing. In other words, problems such as land subsidence in urban areas, rising water and sewage charges due to capital investment for lagging sewage treatment facilities compared to those in Europe and the United States, and water cuts due to specific weather conditions in summer in specific areas Demands for saving flushing water in order to cope with such problems are increasing in recent years, due to the recent increase in the amount of processing at plate-making shops and the problem of total wastewater control.

In response to the water-saving requirements as described above, anhydrous washing / no-pipe systems or counter-current washing that perform chemical treatment instead of the conventionally proposed washing treatment are used for the current black-and-white silver halide photosensitive materials, especially for printing plate making. Automated developing equipment has increased the complexity and size of the processing equipment, such as the number of processing tanks. As a result, the processing line has become longer and the processing time of photosensitive materials has become slower. From the point of view, it was in a completely backward direction and could not be applied.

Therefore, as one method, a method is conceivable in which a water tank for storing washing water is provided in the vicinity of the washing tank separately from the washing tank for performing the washing processing, and the washing water is circulated between the water tank and the washing tank. However, according to this method, the concentration of the components of the developer, fixer, and components eluted from the photosensitive material such as dyes, dyes, surfactants, and gelatin, which are carried into the washing water by the photosensitive material to be processed, are processed. Increase as the volume increases,
In particular, in recent large-scale treatment, the value of iodine consumption as a legally defined water quality preparation exceeds the value of iodine consumption in a short time, leaving a problem in drainage, that is, problems of water saving efficiency and wastewater treatment. At the same time, no satisfactory method has yet been found.

On the other hand, the consumption of silver halide photographic materials has been steadily increasing in recent years. For this reason, the number of developed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time.

One method for shortening the development processing time (generally consisting of development, fixing, washing and drying steps) is to increase the transport speed. However, when developing with a roller transport automatic developing machine, if the roller transfer speed is increased to shorten the developing processing time, the time for the film to be in the water in the water washing process is shortened. Is insufficient, and in particular, residual colors due to dyes and spectral sensitizing dyes resulting from insufficient washing cause deterioration in image quality.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a method for processing a silver halide black-and-white photographic light-sensitive material which enables recycling of washing water, thereby improving water saving efficiency.

A second object of the present invention is to provide a method for processing a silver halide black-and-white photographic material having improved residual color in ultra-rapid processing in which the total processing time is 20 to 60 seconds.

A third object of the present invention is to provide a wastewater treatment method capable of purifying contaminated washing water to the extent that it can be drained.

 Other objects will become apparent in the following specification.

[Configuration of the invention]

The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the object of the present invention can be achieved by the following, and have accomplished the present invention.

(1) In a method for processing a silver halide black-and-white photographic light-sensitive material using an automatic developing apparatus comprising at least a developing section, a fixing section and a water-washing section, a means for the water-washing section to wash at least the light-sensitive material; Water storage means for temporarily storing water containing used washing water discharged from the means as washing water supplied to the washing means, and regenerating means for adding an oxidizing agent to regenerate the used washing water. A circulating means for circulating the rinsing water in the rinsing means and the rinsing water in the water storing means between the rinsing means and the water storing means, and performing a rinsing treatment with the rinsing water in the rinsing means. A method for processing a silver halide black-and-white photographic light-sensitive material, or (2) a method for processing a silver halide black-and-white photographic light-sensitive material using an automatic developing apparatus including at least a developing unit, a fixing unit, and a water-washing unit. Few Water washing means for washing at least the photosensitive material, water storing means for temporarily storing water containing used washing water discharged from the washing means as washing water supplied to the washing means, and the used washing water A regenerating means for adding an oxidizing agent to regenerate water, a circulating means for circulating between the rinsing water in the rinsing means and the water storing means, and a rinsing water circulating by the circulating means having a predetermined concentration of contamination. A cleaning agent supply means for supplying a cleaning agent to the water storage means, a drainage means for draining at least a part of the washing water in the water storage means after the cleaning agent is supplied, and And (3) developing the silver halide black-and-white photographic light-sensitive material using an automatic developing apparatus including at least a developing section, a fixing section and a water-washing section. Who do In the method, it is achieved by the method for processing a silver halide black-and-white photographic material described in the above item (1) or (2), wherein the total processing time is 20 to 60 seconds.

 Hereinafter, the present invention will be described in detail.

As a result of studying a treatment method with excellent water saving efficiency, the present invention and the like have considered the use of an oxidizing agent as a regenerating means for reusing used washing water.

When an oxidizing agent is used, the silver halide photographic material washed with water using the washing water regenerated by the oxidizing agent is developed, fixed, and even in ultra-rapid processing such that the total processing time of water washing is 20 to 60 seconds, It was found that the residual color was reduced.

FIG. 1 is a schematic view schematically showing an example of a washing section of the automatic developing apparatus of the present invention. According to FIG. 1, the washing section of the developing device of the present invention comprises a washing tank 1 for processing the photosensitive material, washing water for replenishing the washing tank 1 and washing water overflowing from the washing tank 1 due to the above replenishment. A water tank 2 provided near the water tank 1 to be stored, and a circulating means for replenishing the water from the water tank 2 to the water tank 1 and supplying overflow water from the water tank 1 to the water tank 2. 3, for example, a filter 4 provided as one of the regenerating means provided in the middle of the path from the water tank 2 to the washing tank 1 and the washing water circulated by the circulating means 3 automatically as a regenerating means. An oxidizing agent supply tank 5 for supplying the oxidizing agent to the oxidizing agent 2; and after the oxidizing agent is supplied, the photographic material is processed again in the rinsing section or the discharging means 6 for discharging at least a part of the rinsing water in the water storage tank 2
And consists of

That is, after the washing tank 1 and the water tank 2 are filled with unused washing water at the start of the development processing, the photosensitive material of the developing and fixing agent is washed with the washing tank 1, and the water is stored in accordance with the processing amount of the photosensitive material. The washing water is automatically replenished from the tank 2 and, as a result, the used washing water overflowing from the washing tank 1 is sent to the water tank 2 without being drained as it is conventionally, and is temporarily stored. As the throughput increases, the circulation is repeated, whereby the washing water in the washing tank 1 and the water tank 2 is brought in by the photosensitive material and eluted from the photosensitive material such as a fixing solution component or dyes, dyes, surfactants, and gelatin. Contamination is caused by the components, and as a result, the washing efficiency is reduced, and the finish of the photosensitive material after the washing is adversely affected. In order to prevent this, for example, a filter 4 is provided between a path from the water tank 2 to the water tank 1 or a path from the water tank 1 to the water tank 2, and a component which adversely affects the photosensitive material from the water, In particular, regeneration treatment of washing water is performed by removing gelatin, scale, dust and the like. As such a filter, carbon fiber, aramid fiber, Teflon resin fiber, hemp, glass fiber, polyethylene foam, polypropylene foam and the like are preferably used as the material of the filter fiber from the viewpoint of heat resistance and chemical resistance. Further, those described as a contact substance in JP-A-60-263151 can also be used.

For example, the filter can be used in combination with a sheet filter made of, for example, activated carbon fiber to prevent clogging or the like due to a gelled substance such as gelatin. It is possible.

As the regenerating means, an oxidizing agent supplying means including an oxidizing agent supplying tank is provided, and the oxidizing agent is supplied to the water storage tank 2 at appropriate times, whereby the washing water can be regenerated.

Examples of such an oxidizing agent include metal or non-metal oxides, oxide acid-based acids or salts thereof, peroxides, compounds containing an organic acid-based compound, and the like. The acid-based acid is sulfuric acid, nitrous acid,
Nitric acid, hypochlorous acid and the like are preferable, and as the peroxide, hydrogen peroxide solution, Fenton's reagent and the like are preferably used. Also, ozone is preferably used.

These oxidizing agents are diluted with water or the like and added to the water storage tank 2 from an oxidizing agent supply tank arranged adjacent to the water storage tank 2, but usually, a fixed amount is automatically added from the supply tank as needed. It is added to the water storage tank 2 in such a manner that the supply valve is opened and automatically dropped at a rate of about once every several hours. The amount of addition can be arbitrarily selected depending on the type of photosensitive material, the amount of processing, the type of processing solution, and the like. In a system in which the required amount is automatically added in units, the molar range is 1/2 mol to several times equivalent mol, especially 1/2 mol to equivalent mol, based on the thiosulfate ion in the fixing solution to be introduced. Is preferably added in the range. In addition, since the fixing liquid component actually introduced is proportional to the processed photographic material, it is possible to determine the addition amount depending on the amount of the processed photographic material. In addition, the water storage tank 2 may have a known stirring means in order to efficiently perform regeneration.

In the present invention, the regeneration means using the oxidizing agent is
The species may be selected and used, or two or more kinds of regenerating means such as the above-described filter processing may be used in combination.

If the amount of treatment further increases and the degree of contamination progresses, it becomes necessary to drain all or at least a part of the washing water in the water storage tank 2 and replace it with fresh washing water. However, in particular, when the degree of contamination exceeds the above-mentioned drainage standard, drainage to the sewer becomes impossible. Therefore, it is necessary to always detect the concentration of the washing water contamination and keep the concentration within an allowable range.
Therefore, the contamination concentration of the washing water is measured by any method, preferably, the washing water in the water tank 2 is measured by using the contamination concentration measuring means, and the cleaning agent supply tank 5 automatically outputs the contamination concentration based on the measured value. A purifying agent is supplied to purify the washing water in the water tank 2 to an allowable value. Thereafter, at least a part of the purified washing water is drained by the drainage means 6. The washing water in the water storage tank 2 may be entirely drained, or only one part may be drained and replaced with fresh washing water to be mixed and used.

In the present invention, the contaminant concentration of the washing water is a fixing liquid component which is considered to have the greatest influence on the iodine consumption since it is considered that it is necessary to satisfy the iodine consumption regulation because the sewerage is discharged. It can be considered as the concentration of thiosulfate ions such as certain ammonium thiosulfate and sodium thiosulfate.

As the purifying agent used in the present invention, the same oxidizing agent as that used as the regenerating means can be used.

Further, when the oxidizing agent supply tank is provided as a regenerating means, the purifying agent supply tank is preferably used in combination with the oxidizing agent supply tank.

For example, when the thiosulfate ion concentration of the washing water in the water tank 2 exceeds the value corresponding to the reference value of the iodine consumption, these purifying agents can be added according to the concentration, and diluted with water or the like. Then, the water is added to the water storage tank 2 from the purifying agent supply tank 5 disposed adjacent to the water storage tank 2, but is usually added automatically from the supply tank as needed in a fixed amount, preferably for several hours. The supply valve is opened at a rate of about one degree and the water is added to the water storage tank 2 in a form of automatically falling. The amount of addition can be determined by experiments or the like according to the thiosulfate ion concentration in the washing water.

As means for supplying a purifying agent in a fixed amount according to the thiosulfate ion concentration and automatically purifying the purifier according to the present invention, OR means
A method is possible in which the ORP value is measured with a P (redox potential) electrode and the purifying agent is automatically added based on the measured ORP value.

Specifically, a predetermined concentration of sodium thiosulfate solution pH 4
Alternatively, the pH is adjusted to 7, sodium hypochlorite is added, and the iodine consumption, KMnO ₄ consumption, and ORP value are measured to determine the amount of the purifying agent added. That is, for example, 0.03N
-When sodium hypochlorite was added to each of pH 4 and pH 7 Na ₂ S ₂ O ₃ solutions, the ORP value of the first wave sharply increased in the pH 7 solution at a certain amount. ,
This coincided with the lowest value of iodine consumption. This is S ₂ O ₃
^2- indicates that the whole amount was oxidized. Further addition of sodium hypochlorite leads to the rise of the second wave of pH 7 solution and pH 4
A sharp rise of the solution is observed. Thus, in the neutral or acidic region, the rise of the ORP value is used to increase the value to +500.
Purification can be performed automatically by adding sodium hypochlorite until it reaches ~ 800 mV. By such a method, the amount of the purifying agent to be added can be determined by measuring the ORP in various cases.

The ORP electrode may be installed in a water storage tank, and may be measured continuously or as needed, or may be measured by inserting the ORP electrode into the water storage tank as needed. Alternatively, the measurement value may be used in a circulation system outside the water storage tank, in a washing tank, or the like, and the measured value may be substituted for the measurement value in the water storage tank.

The measured value is automatically or artificially fed back to the purifying agent supply means, and, for example, by operating an electromagnetic on-off valve or the like, a necessary amount of the purifying agent can be supplied to the flush water in the water storage tank. In the water storage tank, a usual well-known stirring means may be provided to promote purification.

As another method of measuring the concentration of contamination, there is a method of measuring the area of the processed photographic material and substituting it. That is, since thiosulfate ion, which is a main contaminant, is a component carried by the processed light-sensitive material, its amount is considered to substantially correspond to the amount of the processed light-sensitive material, that is, the total area. Therefore,
The concentration of contamination when a predetermined amount of the photosensitive material is processed by an experiment and the amount of the purifying agent required to purify the concentration to a predetermined value are determined in advance, and the processed photosensitive material is used by using the result. May be measured and calculated, and a corresponding amount of the purifying agent may be supplied.

As such a method, specifically, a light-sensitive material is detected by a sensor provided near a light-sensitive material insertion port of an automatic developing machine,
The total area of the processed light-sensitive material is counted by a counter connected to the sensor based on the information of the sensor. When the counted total area exceeds a value corresponding to a predetermined contamination concentration, a predetermined amount of a purifying agent is supplied to the water tank based on the experimental value. At this time, the experimental values are input in advance,
A system for calculating and automatically supplying the amount of the purifying agent corresponding to the total area value may be provided in the apparatus,
When the total area counter exceeds a predetermined value, an alarm sounds, and the alarm may be supplied artificially based on an experiment.
In the water storage tank, a usual well-known stirring means may be provided to promote purification.

By adding the purifying agent as described above, a predetermined value,
At least a part of the washing water purified to at least a value satisfying the drainage standard is drained by the drainage means 6.
The drainage means has, for example, an electromagnetic valve and can be opened and closed automatically. However, the valve may be opened automatically after the supply of the cleaning agent, or automatically or artificially after the supply or purification of the cleaning agent is confirmed. It may open and drain.

As the washing means of the automatic developing apparatus of the present invention, various conventionally known washing tanks and washing methods can be used. Further, water containing various additives known in the art can be used as washing water. In particular, it is effectively used for preventing the generation of water scale in washing water provided with fungicide or in water stagnated in a water tank.

Examples of such antifungal means include an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in JP-A-60-263940, and an ion-exchange resin described in JP-A-61-131632. No. 60-253807, 60
-295894, 61-63030, 61-51396, etc. can be used.

Furthermore, LEWest “Water Quality Criteria” Photo S
ci & Eng. Vol. 9 No. 6 (1965), NWBeach “Microbiolo
gical Growths in Motion-Picture Processing "SMPTE
Journal Vol.85, (1976) .RODeegan, “Photo Process
ing Wash Water Biocides "J.Imaging Tech.Vol.10, No.6
(1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-57-58143.
-105145, 57-132146, 58-18631, 57-9
Antibacterial agents, antibacterial agents, surfactants and the like described in Nos. 7530 and 57-157244 can also be used in combination.

Furthermore, RTKreiman's J.Image, Tech10,
(6) Isothiazoline compounds described in 242 (1984), RESEARCH DISCLOSURE Vol. 205, Item 20526 (1981)
Compounds, described in Vol. 228, Item 22845 (April, 1983), compounds described in Japanese Patent Application No. 61-51396, and the like. Can be used in combination as a bacteriostatic agent (Microbiocide).

Further, specific examples of the anti-binder include phenol, 4-chlorophenol, pentachlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoate,
2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide 2,4,4'-trichloro-
2'-hydroxydiphenyl ether and the like.

In addition, various methods such as processing with stirring, use of a washing accelerator, supply of washing water according to the processing area of the photosensitive material, and use of a squeeze to reduce carryover to the washing tank are also used in combination. can do.

In addition, the ultra-rapid processing referred to in the present specification means that after inserting the leading end of the film into an automatic developing machine, the film passes through a developing tank, a transfer section, a fixing tank, a transfer section, a washing tank, a transfer section, and a drying section. The total time (in other words, the quotient (sec) obtained by dividing the total length of the processing line (m) by the line transfer speed (m / sec)) until the tip of the substrate comes out of the dry portion is 20 seconds to 60 seconds. A certain process. The reason why the time of the transition portion should be included here is well known in the art. However, even in the transition portion, since the liquid of the previous process swells in the gelatin film, it is substantially used. This is because the processing step can be regarded as progressing.

 The details of the present invention are described below.

The silver halide emulsion used in the light-sensitive material of the present invention may be a silver halide emulsion such as silver bromide, silver iodobromide, coin silver, silver chlorobromide, and silver chloroiodobromide. Any of those used can be used. Preferably, a silver chlorobromide containing 60 mol% or more of silver chloride as a negative-working mercury halide emulsion or 10 mol% or more of silver bromide as a positive working silver halide is used. Silver chlorobromide, silver bromide and silver iodobromide. The silver halide grains may be obtained by any of an acidic method, a neutral method and an ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be particles formed mainly in the particles or particles mainly formed inside the particles.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patent 4,
Nos. 183,756, 4,225,666, JP No. 55-26589, and JP-B-55-42737, etc., The Journal of Photographic Science (J.Photgr.Sci) .21. 39 (197
Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be produced by a method described in a document such as 3) and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

Emulsions having any grain size distribution may be used, and emulsions having a wide grain size distribution (referred to as polydisperse emulsions)
May be used, or an emulsion having a narrow particle size distribution (referred to as a monodispersing agent) may be used alone or as a mixture of several kinds. or,
A polydisperse emulsion and a monodisperse emulsion may be used as a mixture.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

Monodisperse emulsions can be obtained with reference to JP-A-54-48521, JP-A-58-49938 and JP-A-60-122935.

The photosensitive silver halide emulsion is not subjected to chemical sensitization,
Although a so-called immature (Primitive) emulsion can be used as it is, it is usually chemically sensitized. For chemical sensitization, the Glafkides or Zelikman et al., Or HF
rieser de Grundlagen del Photography Shen Protesse Mito Silberhalogeniden (Di
e Grundlagen der Photographischen Prozesse mit Sil
berhalogeniden, Akademiche Verlagsgesellschaft, 19
The method described in 68) can be used.

The silver halide grains used in the emulsion of the present invention may be formed by a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt during the process of forming and / or growing the grains. Alternatively, a metal ion can be added using a complex salt, and the metal ion can be contained inside the particle and / or on the particle surface.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. The removal of the salts can be performed according to the method described in Research Disclosure No. 17643.

The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. These dyes can be preferably used in a light-returning photographic material, and it is particularly preferable that the sensitivity to light at 400 nm be at least 30 times the sensitivity to light at 360 nm.

Gelatin is used as a binder of the light-sensitive material used in the present invention. Examples of the binder include gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and homo- or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer can be used in combination.

As the gelatin, lime-treated gelatin, acid-treated gelatin, oxygen-treated gelatin as described in Bulletin of Society of Japan (Bull. Soc. Sci. Phot. Japan) No. 16, page 30 (1966) is used. Alternatively, a hydrolyzate or oxygen hydrolyzate of gelatin can be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkyleon oxides, epoxy compounds and the like are added to gelatin. What is obtained by reacting is used. Specific examples are U.S. Pat.Nos. 2,614,928 and 3,132,945
No. 3,186,846, No. 3,312,553, UK Patent 861,414
Nos. 1,033,189, 1,005,784, JP-B-42-26845
No. etc.

The protein may be albumin, casein, the cellulose derivative may be hydroxyethylcellulose, carboxymethylcellulose, a sulfate of cellulose, or the sugar derivative may be sodium alginate, and the starch derivative may be used in combination with gelatin.

As the graft polymer of gelatin and another polymer, a homopolymer or a copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, and styrene is used as the gelatin. A grafted product can be used. In particular, a graft polymer of a polymer having some compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferable. These examples are described in U.S. Pat.
Nos. 3,625, 2,831,767 and 2,956,884.

In the light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item 17643.
(December 1978) and Vol. 187, Item 18716 (November 1979), and the relevant locations are summarized in the table below.

Examples of the support used in the light-sensitive material of the present invention include a paper laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer), a flexible reflective support such as synthetic paper, cellulose acetate, Examples include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports having a reflective layer provided on these films, and metals.

 Among them, polyethylene terephthalate is particularly preferred.

Further, the surface of these supports can be chemically or physically treated. Examples of the treatment include surface treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. .

In practicing the present invention, an organic desensitizer having a positive sum of the anodic potential and the cathodic potential of a polarograph described in JP-A-61-26041 can also be used.

The light-sensitive material of the present invention can be exposed to light using electromagnetic waves in a spectral region in which an emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (daylight), tungsten lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenon lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, and light emitting diode lights Any known light source such as light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like can be used. JP-A-62-
A favorable result can be obtained by attaching an absorption filter for absorbing a wavelength of 370 nm or less to a UV light source such as 210458 or using a UV light source having an emission wavelength of 370 to 420 nm as a main wavelength.

Exposure time is usually 1 millisecond to 1 second, which is usually used in cameras, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond using a cathode ray tube or a xenon flash tube. It is also possible to give exposures longer than one second. These exposures may be performed continuously or intermittently.

The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general positive, direct positive and the like.

In the present invention, various development processes for black and white by a known method can be used for the development process of the photosensitive material, but it is particularly effective when the process for the photosensitive material for printing which gives high contrast is performed.

In the present invention, in addition to thiosulfate and sulfite, various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardeners, etc. Can be contained. For example, thiosulfates, sulfites are potassium, sodium, and ammonium salts of these acids, and acids are sulfuric acid, hydrochloric acid, nitric acid,
Examples thereof include boric acid, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid, citric acid, malic acid, and phthalic acid. Examples of the salts include salts of these acids such as potassium, sodium, and ammonium. As a fixing accelerator,
Nos. 45-35754, JP-A-58-122535, and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in U.S. Pat. Dextran ethers, crown ethers, diazabicycloundecene, di (hydroxyethyl) butamine and the like. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the chelating agent include nitrilotriacetic acid and aminoacetic acid such as EDTA. As the hardener, chromium alum, potassium alum and other Al compounds can be contained.

In the present invention, the fixing solution preferably contains an Al compound in order to increase the hardening property of the light-sensitive material, and more preferably the content is 0.1 to 3 g / in terms of Al in the working solution.

The concentration of sulfurous acid contained in the fixing solution is preferably 0.03 to 0.4 mol, more preferably 0.04 to 0.3 mol /.

The preferred fixer pH is 3.9-6.5, the most preferred
pH is 4.2-5.3.

〔Example〕

Examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to these.

Example 1 A silver chlorobromide emulsion (containing 65 mol% of silver chloride and 3 mol% of silver bromide) was prepared by an acidic method. The silver halide grains are cubic, monodisperse grains having an average grain size of 0.25 μm and an average grain size of 0.7 to 1.3 times, and containing 90% or more of all grains. For this silver chlorobromide emulsion, a temperature of 60 ° C, 6.0p
Gold sulfur sensitization was performed at H and 170 mV EAg, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. The emulsion was divided, and the following dyes [A], [B] and [C] were added in an amount of 25 per mole of silver halide.
0 mg each was added and spectral sensitization was performed.

Further, 300 mg of sodium p-dodecylbenzenesulfonate per mole of silver halide, 2 g of styrene-maleic acid copolymer, 2 g of styrene-butyl acrylate-acrylic acid copolymer latex (average particle size of about 0.25 μm)
g was added so that the Ag amount was 3.5 g / m ² and the gelatin amount was 2.0 g / m ² , and the photographic emulsion layer was subjected to undercoating described in Example (1) of JP-A-59-19941. And coated on a polyethylene terephthalate film base. At that time, as a spreader of gelatin amount 1.0 g / m ² , 30 mg of 1-decyl-2- (3-isobentyl) succinate-2-sodium sulfonate was used.
/ m ² , and a protective layer containing 25 mg / m ² of formalin as a hardener was applied simultaneously and in layers.

Compounds [A], [B], [C] for the obtained sample
Each of Sample [A], Sample [B] and Sample [C] was exposed with a tungsten light source using an optical wedge.

 The following developer and fixer were used.

(Developer composition)

(Composition A) Pure water 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-phenyl-5 -Mercaptotetrazole 30 mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure 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 700 mg When using a developing solution, the above (composition A) and (composition B) were dissolved in 500 ml of water in this order, and used after finishing to 1 with water.

(Fixing solution formulation)

(Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% W / V aqueous solution) 13.6 ml (Composition B) Pure water 17 ml Sulfuric acid (50% W / W aqueous solution) 4.7 g Aluminum sulfate 26.5 g (Al ₂ O ₃ equivalent content of 8.1% W / W aqueous solution) Make this one finish.

 The pH of the fixing solution was about 4.3.

As the washing section, the supply valve from the water supply to the automatic developing machine is cut off and connected to a water tank made of polyvinyl chloride having a volume of about 50. twenty two
And a total of 62 water was circulated.

Further, a filter cartridge in which Kyoward 600 was attached to polypropylene fiber manufactured by Awa Paper Co., Ltd. was interposed in the middle of a piping route for circulation from the water storage tank to the washing tank, and used for removing gelatin, dust and the like.

Further, as hydrogen peroxide diluted 6% as an oxidizing agent is added to該貯water tank from the oxidant supply tank in proportion of 10.5~10.6CC per area 1 m ² of the processed photographic material.

This value was converted from the amount of the fixing solution component to be introduced, and the system was automated so that it operates to open and close the electromagnetic valve of the oxidant supply tank based on the information of the photosensitive material area detection sensor at the insertion part of the automatic processing machine. .

The above-mentioned sample was continuously processed using the apparatus as described above, a photographic characteristic curve was drawn, and the fog density was measured.

In addition, the samples processed without exposure were overlaid with one another, and the residual color of the film was visually evaluated, and evaluated on a five-point scale. "5" was colorless and "1" was a strong orange-colored residual color. . For general plate making, residual color below "3" is a level that is considered to be a size defect.

Various conditions in development, fixing and washing are as follows.

(Step) (Temperature) (Time) Developing 35 ° C. 15 seconds fixing 35 ° C. 15 seconds washing 18 ° C. 10 seconds Drying 40 ° C. 10 seconds dry thermal heat transfer coefficient 180Kcal / h · m ² · ℃ automatic developing machine installation environment humidity (temperature ) = 23 ° C (relative humidity)
= 40% Each process time includes so-called watari transport time until the next process Dry to Dry time 50 seconds Line speed 2000 mm / min For comparison with the present invention, development, fixing, washing In the washing step, water is supplied to the washing tank at 5 / min.

Ultra-rapid processing was performed under the same developing processing conditions as described above.

 The results obtained are shown in Table 1 below.

Sensitizing dye As is clear from Table 1, when the washing water used in the washing step is circulated and reused, the apparatus of the present invention in which the oxidizing agent is supplied in accordance with the area of the processed photosensitive material and the washing water are used as a means of regeneration. It can be seen that the treatment significantly reduced the reduction of residual color and the occurrence of fog caused by the ultra-rapid processing.

Further, using the apparatus of the present invention and the washing water, the sample [A]
After continuously processing 100 pieces of the four-cut size for [C], the same photographic performance evaluation was performed for the 100th sheet, but the same result was obtained.

When the silver halide photosensitive material sample [A] was continuously treated with circulating washing water by the apparatus of the present invention, the processing area was 20%.
was evaluated for samples as they become m ^2, a value of residual hypo value 0.04 g / m ² to ensure the preservation of the photographic performance ANSI (American, Natinal, Standard, institute),
It was fully guaranteed from the viewpoint of 1985 standard values. Further, in order to evaluate the quality of the water circulating in the present apparatus, when the total treatment area becomes 20 m ² as described above, the iodine consumption value is 200 mg /, and the drainage standard can be satisfied at this point.

Therefore, it was not necessary to add hydrogen peroxide solution for water purification.

〔The invention's effect〕

As described above in detail, the water saving effect is greatly improved by circulating the washing water and supplying the oxidizing agent according to the area of the photographic material to regenerate the water according to the present invention, thereby greatly improving the water saving effect. For a user who is running while running down at / min, it is possible to save water up to about 30 to 1/60, though there is a slight difference depending on the amount of processing photographic material.

Further, by processing using the apparatus of the present invention, a silver halide black-and-white photographic material having excellent ultra-rapid processing characteristics can be obtained.

Further, the automatic developing apparatus of the present invention can provide a processing method for preventing an increase in a residual fixing solution component of a silver halide black-and-white photographic material and providing excellent image characteristics.

Further, the automatic developing device of the present invention can improve the water-saving efficiency and purify the used washing water, which is to be a waste liquid with a high pollution load, to a level at which sewage can be washed. Can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic diagram schematically showing an example of a water washing section of the automatic developing apparatus of the present invention. DESCRIPTION OF SYMBOLS 1 ... Rinse tank, 2 ... Water tank, 3 ... Circulation means 4 ... Filter, 5 ... Purifier supply tank 6 ... Discharge means

Claims (3)

(57) [Claims] 1. A method for processing a silver halide black-and-white photographic material using an automatic developing apparatus comprising at least a developing section, a fixing section and a rinsing section, wherein said rinsing section rinses at least the photographic material with water, Water storage means for temporarily storing water containing used washing water discharged from the washing means as washing water supplied to the washing means, and regeneration for adding an oxidizing agent to regenerate the used washing water Means, and circulating means for circulating the rinsing water in the rinsing means and the rinsing water in the water storing means between the rinsing means and the water storing means, and performing rinsing with the rinsing water in the rinsing means. A method for processing a silver halide black-and-white photographic material. 2. A method for processing a silver halide black-and-white photographic material using an automatic developing device comprising at least a developing section, a fixing section and a rinsing section, wherein said rinsing section comprises at least a rinsing means for rinsing the photographic material. A water storage means for temporarily storing water containing used washing water discharged from the washing means as washing water supplied to the washing means, and an oxidizing agent for regenerating the used washing water. Reproduction means,
A circulating means for circulating between the rinsing water in the rinsing means and the water storing means, and supplying a purifying agent to the water storing means when the concentration of the rinsing water circulated by the circulating means exceeds a predetermined value. A purifying agent supply unit, and a drainage unit that drains at least a part of the washing water in the water storage unit after the purifying agent is supplied, and performs a washing process with the washing water in the washing unit. A processing method for a silver halide black-and-white photographic light-sensitive material. 3. A method for developing a silver halide black-and-white photographic material using an automatic developing apparatus comprising at least a developing section, a fixing section and a rinsing section, wherein the total processing time is 20 to 60 seconds. A method for processing a silver halide black-and-white photographic light-sensitive material according to claim 1 or 2, characterized in that: