JPH09274296A - Method for processing photosensitive material and automatic developing machine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To quicken processing and to reduce waste processing solution without causing a defect associated with the temperature rise of processing solution by providing a means for directly heating photosensitive material and heating the photosensitive material which is being processed. SOLUTION: By energizing an electric heater 13 through a conductor 11, a carrying roller 5 is heated and the heating temperature is sensed by a temperature sensor 17 and controlled. Heat energy necessary for development is directly supplied to the photographic sensitive material in a developing bath or carried between the developing bath and a next processing bath by the roller 5. Thus, high developing activity necessary for rapid development is obtained and the swelling of a photosensitive layer is accelerated, so that the processing is quicked. Since the temperature of developer in the developing bath is low, the developer in the developing bath is hardly oxidized by air. Even when the developer retains in the developing bath for a long time, the air oxidation of the developer is prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a light-sensitive material and an automatic processor, and more particularly to a processing method and an automatic processor suitable for photographic processing of a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Photographic processing of a light-sensitive material, for example, a silver halide photographic light-sensitive material is carried out in the case of a black-and-white light-sensitive material, an X-ray light-sensitive material, etc. In the case of a light-sensitive material, it is carried out by processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water and stabilization. In a photographic process for processing a large amount of light-sensitive material, an automatic processor is used, and usually, a replenisher is replenished with the process solution, and a part of the process solution is discarded as a waste solution out of the system. The performance of is kept constant.

In recent years, regulations on environmental pollution have been strengthened, and it is impossible to dispose of a waste liquid of a processing liquid to a sewer or a river, and it is not possible to increase the amount of the waste liquid. It is desired to reduce the amount of replenisher.

Further, in order to meet a user's request to see a finished photograph quickly, photographic processing has been speeded up. In particular, in medical light-sensitive materials, regular medical examinations and medical checkups have become widespread, and inspections in general medical care have been rapidly increasing, so that more rapid photographic processing is required.

In order to carry out photographic processing quickly and shorten the processing time, it is necessary to increase the processing speed and carry out development, fixing, washing with water and the like in a short time.

In order to increase the developing speed, methods such as increasing the amount of the developing agent, raising the pH of the developing solution and raising the developing temperature can be considered.

However, in any of the methods, although the developing speed is high, the reactivity of the developing solution is high, so that the developing solution is susceptible to air oxidation and the life of the developing solution is shortened. . Furthermore, if the replenishment amount is reduced in order to reduce the amount of waste liquid, the developing solution stays in the processing tank for a longer time, which makes it more susceptible to air oxidation.

In order to prevent air oxidation of the developer, a method of adding sulfite, ascorbic acid, polyhydroxybenzenes or the like as a preservative has been conventionally used. It was not sufficient to prevent air oxidation and prolong the life of the developer.

Further, the same applies to the fixing solution. The higher the temperature, the better the fixing performance can be obtained. Therefore, in order to increase the fixing speed, it is conceivable to raise the temperature of the fixing solution.

However, the fixing solution contains a fixing agent and
It contains sulfurous acid, which is a preservative of the fixing agent, and acetic acid, etc., as a buffering agent. When the temperature of the fixing solution is raised, the odor generated from these becomes severe and there is a problem. Further, there is a problem that the fixing agent is decomposed, the life of the fixing solution is shortened, and the waste solution is increased.

Therefore, it has been required to shorten the developing time without shortening the life of the developing solution and to shorten the fixing time while reducing the generation of odor.

Further, it is not preferable from the viewpoint of energy cost to always keep the liquid temperature of the developing solution and the fixing solution high.

With respect to the rinsing water used for rinsing as well, the higher the temperature, the better the rinsing performance can be obtained. However, since a large amount of rinsing water is used, it is necessary to use hot rinsing water in terms of energy cost. Even looking at it, it was not preferable.

In the case of the developing solution and the fixing solution, it is also necessary to keep the temperature of the developing solution and the fixing solution high.
It is not preferable from the viewpoint of energy cost.

[0015]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for processing a light-sensitive material which can speed up the processing and reduce the amount of processing waste liquid without causing a defect due to the temperature rise of the processing liquid. To do.

Further, an object of the present invention is to provide an automatic developing machine for a light-sensitive material capable of speeding up the processing and reducing the amount of processing waste liquid without causing a defect due to the temperature rise of the processing liquid. Especially.

[0017]

The above-mentioned objects of the present invention are as follows: (1) In a method of processing a photosensitive material, in which the photosensitive material is conveyed, immersed in a processing bath, and subjected to photographic processing, a means for directly heating the photosensitive material is provided and during processing. A method for processing a photosensitive material, comprising heating the photosensitive material. (2) The method for processing a photosensitive material according to the above (1), wherein the photosensitive material is conveyed using a conveying roller. (3) The method for processing a light-sensitive material according to the above (1) or (2), wherein the light-sensitive material is heated by a carrying roller having a heater. (4) The method for processing a light-sensitive material as described in (1) to (3) above, wherein the light-sensitive material is heated with a heating plate. (5) The method for processing a light-sensitive material as described in (1) to (4) above, wherein the light-sensitive material is heated in a developing bath. (6) The method for processing a light-sensitive material as described in (1) to (5) above, wherein the light-sensitive material is heated in a fixing bath. (7) The method for processing a light-sensitive material as described in (1) to (6) above, wherein the light-sensitive material is heated in a washing bath. (8) The method for processing a light-sensitive material as described in (1) to (7) above, wherein the light-sensitive material is heated between processing baths. (9) The method for processing a photosensitive material according to the above (1) to (8), wherein the developing time is 4 seconds or more and 14 seconds or less. (10) The processing method according to the above (1) to (9), wherein the replenishment amount of the developer is 30 cc / quarter or less. (11) The method for processing a light-sensitive material according to the above (1) to (10), wherein the fixing time is 3 seconds or more and 10 seconds or less. (12) In an automatic developing machine for a photosensitive material having a transport mechanism for transporting the photosensitive material and a photographic processing tank, a means for directly heating the photosensitive material is provided between the first photographic processing tank and the final photographic processing tank. An automatic developing machine for photosensitive materials. (13) The automatic developing machine for photosensitive material as described in (12) above, wherein the transport mechanism for transporting the photosensitive material is a transport roller. (14) The automatic developing machine for photosensitive material as described in (12) or (13) above, wherein the means for directly heating the photosensitive material is a roller having a heater. (15) The automatic developing machine for a light-sensitive material according to the above (12) to (14), wherein the rollers having a heater are arranged in a zigzag pattern. (16) The automatic developing machine for photosensitive material according to the above (12) to (15), wherein the means for directly heating the photosensitive material is a heating plate. (17) A roller having a heater is provided in the photographic processing tank, wherein the rollers are provided (12) to (1).
6) An automatic processor for the light-sensitive material described in 6). (18) The above-mentioned (12) to (1), wherein the photographic processing tank provided with a roller having a heater is a developing tank.
7) An automatic developing machine for the light-sensitive material as described above. (19) The above-mentioned (12) to (1) wherein the photographic processing tank provided with a roller having a heater is a fixing tank.
8) An automatic processor for the light-sensitive material described in 8). (20) The above-mentioned (12) to (1), wherein the photographic processing tank provided with a roller having a heater is a washing tank.
9) An automatic developing machine for the light-sensitive material as described above. (21) A conveyance roller having a heater is provided between the photoprocessing tanks (12) to (12) above.
(20) An automatic developing machine for a light-sensitive material according to the above item. (22) The above-mentioned (12), wherein a roller having a heater is provided between the developing tank and the fixing tank.
An automatic developing machine for a light-sensitive material according to (21). (23) A roller having a heater is provided between the fixing tank and the water washing tank, which is characterized in (12) above.
(22) An automatic developing machine for a light-sensitive material according to (22). Is achieved by

The present invention is intended to speed up photographic processing while keeping the temperature of the processing solution low by directly supplying the heat energy required for carrying out photographic processing reaction directly to the photographic light-sensitive material to be conveyed. Is.

For example, in the development, the photographic light-sensitive material conveyed in the development bath or between the development bath and the next processing bath is directly supplied with the heat energy required for the development by a conveyance roller or the like to rapidly develop the development. The high development activity necessary for the development is obtained, and the swelling of the photosensitive layer is promoted, resulting in speeding up of the processing, and because the developer temperature in the developing bath is low, air oxidation of the developing solution in the developing bath is carried out. As a result, the airborne oxidation of the developing solution can be prevented even if the developing solution stays in the developing bath for a long period of time. In fixing, the heat energy necessary for fixing is directly supplied to the photographic light-sensitive material conveyed in the fixing bath or between the fixing bath and the next processing bath by a conveying roller or the like, which is necessary for rapid fixing. High reactivity is obtained and swelling of the photosensitive layer is promoted, resulting in speeding up of processing, and because the fixing bath temperature in the fixing bath is low, decomposition of the fixing bath in the fixing bath is prevented and odor is eliminated. Can be reduced. The same applies to other processing.

Hereinafter, the present invention will be described in detail.

The photographic process (hereinafter sometimes referred to as developing process) means a process for forming an image by subjecting an exposed photosensitive material to a series of processes. Depending on the photosensitive material to be processed, black and white development, color development, stop,
It includes bleaching, fixing, stabilizing and other processing.

The method of processing a light-sensitive material and the automatic developing machine of the present invention may process any kind of light-sensitive material without any limitation. For example, whether a negative film is processed, a positive film is processed, a photographic paper is processed, an X-ray film is processed, a photosensitive lithographic plate is used. It may be a printing plate.

The method for processing a light-sensitive material and the automatic developing machine of the present invention will be described below by taking an automatic developing machine for medical X-ray film as an example.

In FIG. 1, 1 is a developing tank, 2 is a fixing tank,
3 is a washing tank, 4 is a squeeze part, 5 is a roller for transportation,
6 is a drying section, 7 is a processing rack for each process, 8 is a film inlet, and 9 is a film outlet.

By the roller 5 for conveyance, the developing tank 1,
The fixing tank 2 and the water washing tank 3 are conveyed and processed.

In the present invention, the developing tank 1, the fixing tank 2,
A roller 5 for transportation, which is immersed in the treatment liquid of the washing tank 3.
Some or all of the rollers 5 for transportation between the tanks which are not immersed in the treatment liquid of these tanks are rollers 5 for transportation having a heater.

FIG. 2 is an explanatory view for explaining the carrying roller 5 having a heater.

In FIG. 2, 11 is a conducting wire, 12 is a roller body, 13 is an electric heater, 14 is a gear, 15 is a hollow shaft, 16 is a bearing, and 17 is a temperature sensor.

The transport roller 5 is heated by energizing the electric heater 13 through the conductive wire 11, and the heating temperature is detected and controlled by the temperature sensor 17.

Although the present invention has been described above by taking the automatic developing machine for medical X-ray film as an example, the present invention is not limited to the above description.

In the above example, the photosensitive material is heated by the transporting roller 5 having a heater. However, other heating means such as a heating plate may be used as a means for directly heating.

The means for directly heating the light-sensitive material is not particularly limited, but a heating means in which an electric heater is incorporated inside the heating body and a heating means in which hot water is circulated inside the heating body are easy and inexpensive and are preferable.

The temperature of the processing bath such as the developing bath and the fixing bath is 15 ° C.
~ 40 ℃ is preferable, more preferably 20 ℃ ~ 35
° C. The temperature of the means for directly heating the photographic material is preferably 2 ° C. or higher, more preferably 10 ° C. to 100 ° C. higher than the temperature of the processing bath.

The range in which a means for directly heating the photosensitive material such as a carrying roller having a heater is provided varies depending on the temperature of the processing bath, the flow rate of the processing liquid flowing through the processing bath, the composition of the processing liquid, the heating temperature, etc. It is not possible to specify the heating range, but usually 5% to 80% of each treatment step
% Is preferably used, more preferably 20% of the processing steps
~ 40%.

In photographic processing, the amount of waste liquid can be reduced by reducing the amount of replenishment.
If it is cut into cc / quarter or less, the residence time of the developer in the developing tank becomes long, and the developing agent undergoes air oxidation to shorten the life of the developer, but the effect of the present invention is as follows. The present invention is suitable for photographic processing with a low replenishment amount of 30 cc / quarter or less because it can be obtained even when the replenishment amount is low. The quarter is a photosensitive material having a size of 10 inches × 12 inches.

The material used for the means for directly heating the photosensitive material such as a carrying roller having a heater is not particularly limited, but a material that easily transfers the heat of the built-in heater to the photosensitive material is used. preferable. Further, a material which is strong against acid and alkali chemicals is preferable. As these materials,
For example, thin stainless steel, or thin stainless steel coated with a material such as a polymer such as tetrafluoroethylene resin, rubber, glass, or bake is preferably used.

Processing steps and processing agents are different depending on the kind of the light-sensitive material of the present invention. For example, a black-and-white film has development, fixing, washing and drying steps, and a color film has a color development step, a bleaching and fixing step or a bleach-fixing step. The washing process may include several steps, and the rinsing process may be required to eliminate the washing process.

In the present invention, the heating of the light-sensitive material by means of directly heating the light-sensitive material can be basically carried out in any step as long as the processing step accelerates the heating. Further, there is no limitation depending on the constitution of the treatment liquid in each step.

Hereinafter, a black and white silver halide photographic light-sensitive material as a light-sensitive material, for example, for printing, medical use, black-and-white general use,
The processing method of the light-sensitive material and the automatic processor of the present invention will be described by taking a silver halide photographic light-sensitive material used for a laser imager or a scanner as an example, but the present invention is not limited to these descriptions.

Although there is no particular limitation on the constitution of the treatment liquid for the purpose of the present invention, the constitution of the treatment liquid preferably used will be described below.

As a developing agent for the developing solution, Japanese Patent Laid-Open No. 4-16464
The dihydroxybenzenes, 3-pyrazolidones described in JP-A No. 1-16841 and JP-A No. 4-16841 can be used in combination. Also, para-aminophenols and 3-aminopyrazolones may be used.

In addition to this, LFA Mason Photographic Proce
226-229 of ssing Chemistry (Focal Press, 1966)
Those described on pages and the like can be used.

The total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones in the developer is
It is preferably 0.1 mol / liter or less.

A preservative is used in the developer. As these preservatives, sulfites, for example, potassium sulfite,
Examples thereof include sodium sulfite, lithium sulfite, ammonium bisulfite, sodium bisulfite, potassium metasulfite, reductones such as piperidinohexose reductone. The amount of these preservatives used is preferably
It is 0.1 to 2.0 mol, more preferably 0.1 to 1.0 mol. When the developing solution is a concentrated developing solution, the amount is preferably up to 3.0 mol per liter of the developing solution. Also, addition of a large amount of ascorbic acids leads to processing stability.

An alkaline agent is used as a pH adjusting agent in the developing solution. Examples of these alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

Further, the developing solution contains buffers such as borate described in JP-A-61-28708, saccharose described in JP-A-60-93439, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate. Agents may be used. These buffers are used so that the pH of the developer is 9.0 to 13, preferably pH 10 to 12.5.

In the developing solution, as a dissolution aid, for example, polyethylene glycols and their esters,
As the sensitizer, for example, a quaternary ammonium salt, a development accelerator, a hardener, a surfactant and the like can be contained. Further, as an anti-sludge agent, for example, JP-A-56
-106244, a silver stain preventing agent, Japanese Patent Application Laid-Open No. 3-51844, sulfides, disulfide compounds, Japanese Patent Application No. 4-92.
The cystine derivative and the triazine compound described in the specification of No. 947 may be contained.

An antifoggant may be added to the developing solution, for example,
Indazole-based, imidazole-based, benzimidazole-based, triazole-based, benztriazole-based, tetrazole-based, thiadiazole-based compounds and the like may be used.
Moreover, you may use sodium bromide, potassium bromide, potassium iodide etc. as an inorganic inhibitor. In addition, L.
F. A Menthon's "Photographic Processing Chemistry" published by Focal Press (1966)
226-229, U.S. Pat.No. 2,193,015, 2,592,3
The antifoggants described in JP-A-64-64, JP-A-48-54933 and the like may be used.

As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid,
For example, as the organic chelating agent, a chelating agent having a chelate washing constant with iron of 8 or more described in JP-A 1-193853 is preferably used. Further, as an inorganic chelating agent, sodium hexametaphosphate, calcium hexametaphosphate,
Polyphosphate or the like is used.

The pH of the developer is preferably 9.0 to 12, and more preferably 9.0 to 11.5. The above-mentioned alkaline agent and buffer agent are used to adjust the pH.

The development is preferably performed for 4 to 14 seconds, more preferably 8 to 9.8 seconds.

The total treatment time is preferably 20 to 33 seconds, more preferably 23 to 30 seconds.

The replenisher for the developing solution is composed of the same components as the developing solution, and replenishes the processing fatigue and oxidation fatigue. As the replenishment method, the width described in JP-A-55-126243, the replenishment by the feed rate, the area replenishment described in JP-A-60-104946, and the control by the number of continuously processed sheets described in JP-A-1-149156 are controlled. There is a supplementary area. The preferred amount of replenishment is
It is 500 to 150 ml per 1 m ^{2 of the} light-sensitive material.

As the fixer, a commonly used fixer can be used, for example, an aqueous solution containing thiosulfate. The pH of the fixer is 3.8 or higher, preferably 4.2-5.
5

As a fixing agent, ammonium thiosulfate,
There are thiosulfates such as sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed.

The fixing solution may contain a fixing hardener such as an aluminum salt.

The concentration of thiosulfate in the fixing solution is preferably in the range of 0.1 to 5 mol / l, more preferably 0.8 to 3 mol / l.

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 fixing is preferably performed in 3 to 10 seconds.

A surfactant may be added to the fixing solution.
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. Is 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 sulfuric acid, hydrochloric acid, nitric acid,
Examples thereof include salts of inorganic acids such as boric acid, organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

As the salt, for example, lithium of the above acid,
Examples thereof include salts such as 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 such as sulfuric acid, boric acid, aminopolycarboxylic acids and salts are preferable. The preferable additive amount of the additive is 0.5 to 20 g / liter.

A water washing zone can be provided in the automatic processor.

Drying is usually carried out at 35 to 100 ° C., preferably 40
It is performed by blowing hot air of ~ 80 ° C or irradiating far infrared rays. The automatic developing machine can be provided with a drying zone provided with these heating means.

In the automatic processor, as described in JP-A-3-264953, water or an acidic solution having no fixing ability is attached to the light-sensitive material during the steps of development, fixing and washing. A mechanism for applying the rinse liquid may be provided. further,
The automatic developing machine may have a built-in device capable of preparing a developing solution, a fixing solution, and a replenishing solution thereof.

The silver halide photographic light-sensitive material is usually composed of a silver halide emulsion layer, a protective layer, an intermediate layer, an antihalation layer, a filter layer, an antistatic layer and the like, and the constituent layers are hydrophilic colloid layers. There is.

Examples of the hydrophilic colloid used in the hydrophilic colloid layer include gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins,
Examples thereof include hydrophilic colloids generally used in the field of photography such as polyvinyl compounds containing polyvinyl alcohol derivatives and acrylamide polymers.

A dispersed polymerized vinyl compound may be added to each of these layers. Suitable compounds of this kind which can improve the dimensional stability of the silver halide photographic light-sensitive material include alkyl acrylate, alkyl methacrylate, acrylic acid, phosphoacrylate,
It includes water-soluble monomers produced by polymerizing vinyl-based monomers such as sulfoalkyl methacrylate.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material may contain a hardener. The hardener controls the expansion rate of the hydrophilic colloid layer.

The swelling ratio of the hydrophilic colloid layer of the silver halide photographic light-sensitive material to water is preferably 200% or less, more preferably 150% or less.

The swelling ratio of the hydrophilic colloid layer to water is
Light-sensitive materials stored at 38 ° C and 50% relative humidity for 3 days at 21 ° C
The amount of change in the thickness of the coating film when immersed in distilled water for 3 minutes is expressed as a percentage compared with that before immersion.

The required swelling ratio can be obtained by adjusting the type and amount of the hardener used.

The hardener used is not particularly limited, and a known photographic hardener can be used by a known method.

The silver halide emulsion grains of the silver halide photographic light-sensitive material may be twin crystals or normal crystals. The crystal habit of the normal crystal grains may be cubic, octahedral, tetrahedral, tetrahedral, or 36-faced, or any of these grains may have a rounded shape. Further, silver halide emulsion grains having an aspect ratio of 2 to 20 are preferably used. A more preferable aspect ratio is 2 to 15, and more preferably 2 to 8.

The silver halide composition of the silver halide grains is
Silver iodobromide is particularly preferable, but silver bromide, silver chloroiodobromide, silver chloride and the like are also preferably used.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method.
For example, Research Disclosure (RD) No.176
43 (Dec. 1978) Pages 22-23, 1. Emulsion manufacturing method (Emulsion
Preparation and types) and the same (RD) No.18716 (19
It can be prepared by the method described on page 648.

Also, “The theOry of the” by TH James
photographic process "4th edition" by GFDauffin "Photographic emulsion Chemistry" Foc
Published by al press (1966), P. Glafkides "Physics and Chemistry of Photography""Chimi et physique photographique" Paul
"Making and coating photographic e" by VL Zelikman et al., Published by Montel (1967).
It is prepared by the method described in “Mulsion” Focal press (1964).

In the silver halide emulsion, tabular silver halide grains preferably account for 50% or more of the total silver halide grains, more preferably 60% or more, and particularly preferably.
70% or more.

As the tabular silver halide emulsion grains, those having monodispersity are preferably used, and those containing 50% or more of silver halide grains contained in a grain size range of ± 20% around the average grain size. Are particularly preferably used.

The silver halide grains may be those in which at least 40% by weight or the number of grains are substantially cubic or tetradecahedral grains, and the apex of the crystal surface is round. .

The size of silver halide grains is not limited, but those having a grain size of 0.95 to 2 μm are preferable.

The silver halide grains are those of 0.7 μm or less.
It is preferable to contain 80% or more. The size distribution of the silver halide grains used in the present invention may be monodisperse or polydisperse, but monodisperse is preferable. Here, the monodisperse means the size distribution of silver halide grains in which 95% of the grains have a size within 40% of the number average grain size. The number average particle diameter is the number average diameter of the projected area of the particles.

These silver halide emulsions are used in the stage of physical ripening or in the stage of grain preparation such as cadmium salt, lead salt, zinc salt, thallium salt, iridium salt, or complex salt thereof, rhodium salt or complex salt thereof, iron salt, Alternatively, a complex salt thereof or the like may be added.

The internal structure of the silver halide grains is arbitrary, but a core / shell structure having a different silver halide composition is preferred.

The silver halide emulsion can be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. For example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, an aggregating polymer agent described in JP-A-2-7037, exemplified G-3, G-8, etc. The method used is mentioned as a particularly preferable desalting method.

To the silver halide emulsion, various photographic additives can be added in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (1978 12
No. 18716 (November 1979) and No. 308119 (198)
The compound described in December, 9) is mentioned. The types of compounds shown in these three RDs and the places where they are described are listed below.

[0091]

[Table 1]

The support which can be used in the light-sensitive material of the present invention is, for example, 28 of RD No. 17643 mentioned above.
And those described in the left column of page 647 of RD No. 18716.

A suitable support is a polyethylene terephthalate film or the like. The surface of these supports is provided with an undercoat layer, corona discharge or ultraviolet irradiation to improve the adhesion to the coating layer. May be.

[0094]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 At the time of development processing, a carrying roller arranged in a zigzag pattern on a developing rack of an automatic developing machine SRX-503 [manufactured by Konica Corporation] was used as a carrying roller (outer diameter) having a heater shown in FIG. (Uses a hollow shaft 15 with a diameter of 24 mm and an inner diameter of 23 mm)
Change to, double the transport speed, Dry to Dry,
An automatic processor modified to convey the film in 23 seconds was used.

A film prepared as follows was used as a light-sensitive material. As the developing solution, the developing replenishing solution and the fixing solution, the developing solution, the developing replenishing solution and the fixing solution prepared as described below were used, and the developing treatment was carried out at the developing solution temperature and the conveying roller temperature shown in Table 2.

A sample film to be developed was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corp.) and irradiated with X-rays at a tube voltage of 90 kVP and 20 mA for 0.05 seconds at different distances. Sensitometric curve by the distance method was prepared by using, and the sensitivity and fog were obtained. The sensitivity is
The logarithm of the reciprocal of the X-ray dose required to obtain the density of fog +1.0 was obtained, and the sensitivity was evaluated as a relative value when the sensitivity under No. 1 condition was 100. Table 2 shows the obtained results.

Further, under the conditions of No. 1, No. 5 and No. 6, 30 sheets (quarter cut, size of 10 inch × 12 inch) were developed continuously for 1 month. The replenishment amount of the developing replenisher was cut into 10 cc / quarter, and the replenisher of the fixing replenisher was cut into 10 cc / quarter. The automatic processor was energized for 8 hours / day to maintain the temperature of the processing tank. Room temperature was 20 ° C. After development for one month, the relative sensitivity and fog were determined in the same manner as above. Table 3 shows the obtained results. For reference, Table 3 also shows the sensitivity and fog obtained at the start of running.

Preparation of Film [ Preparation of Seed Emulsion (T-1)] Solution A ₁ Hydrogen peroxide-treated ossein gelatin 150 g Potassium bromide 60 g Water to make 1000 ml. To 2000 milliliters ₁ solution of silver nitrate 1.5kg water B. Solution C ₁ Hydrogen peroxide treated ossein gelatin 40 g Potassium bromide 1050 g Water to 400 ml. Solution D ₁ Ammonia water (28%) 117.5 ml To solution A ₁ vigorously stirred at 40 ° C., solution B _{1 and} solution C ₁ were added by the double jet method to generate nuclei. After addition, 300
The temperature of the mixed solution was lowered to 20 ° C. by adding milliliter of water, the potential was adjusted to 40 mV, the D ₁ solution was added in 20 seconds, and the mixture was aged for 5 minutes.

After that, the pH was adjusted to 6.0 and then desalting was carried out using a sodium naphthalenesulfonate-formaldehyde resin and an aqueous magnesium sulfate solution to obtain a seed emulsion (T-1).
Was prepared.

When the seed emulsion thus obtained was observed with an electron microscope, it was a monodisperse silver bromide emulsion having an average grain size of 0.25 μm and a broad distribution of 30%.

[Preparation of Silver Halide Emulsion (Em-1)] Solution E ₁ Hydrogen peroxide-treated ossein gelatin 37 g Polypropyleneoxy-polyoxyethylene succinate disodium salt (10% methanol solution) 10 ml The above seeds Emulsion (T-1) 1.14 mol equivalent Make up to 4000 ml with water. Solution F ₁ Osei Gelatin 26 g Potassium bromide 151 g Potassium iodide 23 g Water to 1103 ml.

Solution G ₁ Ossein gelatin 96.5 g Potassium bromide 6248 ml Make up to 4096 ml with water. To 624 milliliters H ₁ solution of silver nitrate 1132g water.

To the E ₁ solution vigorously stirred at 75 ° C., the F ₁ solution and the H solution were added.
_One solution was added by the double jet method. During this time the pH is constant
Kept at 6.5.

After the addition was completed, the pH was adjusted to 6.0 and then 5,5'-dichloro-9-ethyl-3, a spectral sensitizing dye, was added.
Anhydrous salt of 3'-di- (sulfopropyl) oxacarbocyanine sodium salt (sensitizing dye A) was added in an amount of 300 mg per mol of silver halide, and after sufficiently adsorbing, it was removed by the same method as in the above seed emulsion. Salting was performed to prepare a silver halide emulsion (Em-1) composed of planographic twin crystals.

The resulting silver halide emulsion had a pAg of 9.0,
The pH at 40 ° C was 5.85. Further, the obtained silver halide emulsion was observed by an electron microscope to find that the average grain size was 0.
The tabular silver halide grains had a size of 85 μm and a distribution of 20%, the aspect ratio was 2.4, and the average grain thickness was 0.12.

[Preparation of Emulsion Coating Solution] Spectral sensitizing dyes 5, 5'- were added to the obtained silver halide emulsion (Em-1) immediately before the addition of the chemical sensitizer consisting of hypo and chloroauric acid. Di (butoxycarbonyl) 1,1'diethyl-3,3'-di-
(4-Sulfobutyl) benzimidazolocarbocyanine sodium salt anhydride (sensitizing dye B) was added to silver halide 1
After adding 15 mg per mol and performing chemical ripening, 300 mg per mol of silver halide was added with potassium iodide to stop the chemical ripening. Further, 2.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer per mol of silver halide.

To the silver halide emulsion which had been chemically ripened, the following various additives were added per mol of silver halide.

The following additives were added to the above emulsion in the following amounts per mol of silver halide to prepare an emulsion coating solution.

T-butyl-catechol 400 mg styrene maleic anhydride copolymer 2.5 mg nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-dihydroxybenzene-4-ammonium sulfonate 4 g n-C ₄ H ₉ OCH ₂ CH ( OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1,1-dimethylol-1-bromo-1-nitromethane 20 mg

[0110]

Embedded image [Preparation of Protective Layer Solution] The protective layer solution was prepared by adding the following amounts of additives to 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 40 mg Colloidal silica having an average particle size of 0.013 μm 70 mg Glyoxal 50 mg

[0112]

Embedded image The above emulsion coating solution and protective layer solution were coated on the undercoated support and dried to prepare a film A.

Preparation of Processing Solution The developing solution, starter and fixing used in the present invention were prepared with the following compositions. Developer formulation Part-A (for finishing 10.8 liters) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetriamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 1-Phenyl-5-mercaptotetrazole 15 mg 5-Methylbenzotriazole 150 mg Hydroquinone 280 g Add water to make 3600 ml.

Part-B (for finishing 10.8 liters) Glacial acetic acid 150 g Triethylene glycol 144 g 1-phenyl-3-pyrazolidone 19.5 g 5-Nitroindazole 0.32 g n-acetyl-D, L-penicillamine 0.11 g Starter (1.0 liter finishing) Glacial acetic acid 138 g Potassium iodide Amount shown in Table 2 Potassium bromide Amount shown in Table 2 5-methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Water was added. To 1.0 liter.

Add 3 liters of water to Part-A and stir after stirring.
rt-B was added, and water was further added to make 10.8 liter,
Used as a developing replenisher. The pH of the developing replenisher was 10.50.

20 ml of a starter was added to 1 liter of the above-mentioned developing replenisher to prepare a developing solution which was initially placed in the developing tank. PH is 10.30 after adding starter
Met.

Fixer formulation Part-A (for finishing 16.4 liters) Sodium thiosulfate (70wt / vol%) 4100g Sodium sulfite 410g Sodium acetate 250g Glacial acetic acid 365g Tartaric acid 52.5g Boric acid 82g Aluminum sulfate 156g Add water to make 5000ml .

Add water to Part-A to 16.4 liters,
Used as fixer and fixer replenisher. The pH of the fixer was 4.55.

[0119]

[Table 2]

[0120]

[Table 3]

As is clear from Tables 2 and 3, according to the present invention, the same sensitometric performance as the conventional one can be obtained even at a low developer temperature. Further, the developing solution is less susceptible to air oxidation due to the low developing solution temperature, and the stability due to running is improved. Even when the developing temperature was 35 ° C, when the replenishment amount was 32 cc / quarter, the sensitivity did not decrease during running.

Example 2 At the time of development processing, a transport roller (two pairs of opposing rollers) of a rack (watari rack) between a developing tank and a fixing tank of an automatic processor SRX-503 [manufactured by Konica Corporation] (watari roller) A transfer roller having a heater shown in FIG. 2 (using a hollow shaft 15 having an outer diameter of 24 mmφ and an inner diameter of 23 mmφ)
Was used, and the transport speed was doubled in the same manner as in Example 1, and an automatic developing machine modified to transport the film in Dry to Dry in 23 seconds was used.

The film described in Example 1 was used as the photosensitive material. Further, the developing solution, the developing replenishing solution, and the fixing solution described in Example 1 are used as the developing solution, the developing replenishing solution, and the fixing solution.
Development was performed at the developer temperature and the transport roller temperature shown in Table 4.

Also, in the same manner as in Example 1, the sensitivity at the start of running and after the development treatment for 1 month was measured as Sample No.
It evaluated by the relative value when 7 was set to 100. Table 4 shows the obtained results.

[0125]

[Table 4]

As is clear from Table 4, according to the present invention, the same sensitometric performance as the conventional one can be obtained even at a low developing solution temperature. Further, the developing solution is less susceptible to air oxidation due to the low developing solution temperature, and the stability due to running is improved.

Example 3 In the development processing, the carrying rollers arranged in a zigzag pattern on the fixing rack of the automatic developing machine SRX-503 [manufactured by Konica Corporation] were replaced with the carrying rollers having the heater shown in FIG. (Uses a hollow shaft 15 with an outer diameter of 24 mmφ and an inner diameter of 23 mmφ)
Was used, and the transport speed was doubled in the same manner as in Example 1, and an automatic developing machine modified to transport the film in Dry to Dry in 23 seconds was used.

The film described in Example 1 was used as the light-sensitive material. Further, the developing solution, the developing replenishing solution, and the fixing solution described in Example 1 are used as the developing solution, the developing replenishing solution, and the fixing solution.
At the fixing solution temperature and the transport roller temperature shown in Table 5, the film (cut into four, size of 10 inches x 12 inches) is 30 per day.
00 sheets were developed.

After processing 3,000 films, residual silver, residual color, odor, and decomposition of the fixing agent were evaluated as follows. Table 5 shows the obtained results.

<< Evaluation of Amount of Residual Silver >> After processing 3000 films, the unexposed film was developed, and the resulting processed film contained an aqueous solution containing 2.6 × 10 ⁻³ mol / liter of sodium sulfide (evaluation of residual silver). Solution), leave it for 3 minutes, and then wipe off the residual silver evaluation solution and dry it. The concentration of the produced silver sulfide is measured by a photographic densitometer PDA-65 using a 436 ± 10 nm interference filter as a spectral filter. (Manufactured by Konica Corporation) was used to measure the light transmission density, and the amount of silver remaining in the film was evaluated based on the difference in light transmission density between the portion where the residual silver evaluation liquid was dropped and the portion where the residual silver evaluation liquid was not dropped.

The larger the difference in light transmission density, the higher the residual silver density in the film.

<< Evaluation of Residual Color >> After processing 3000 films, the unexposed quadrant size film was processed in the same manner, and the processed film was processed at a color temperature of 7700 Kelvin and an illuminance of 11
It was visually evaluated by transmitted light on a light source stand of 600 lux according to the following evaluation criteria.

Evaluation Criteria A: No Dye Residue B: Dye Residue Slightly but Does Not Hinder Diagnosis C: Dye Residue is Appreciable from Diagnostic Point D: Dye Residue is Clearly Present There is a problem in diagnosis

<< Evaluation of Odor >> After processing 3000 films, a fixing solution was sampled to evaluate the intensity of odor. ◯: Little odor Δ: Odor but not so bad X: Strong odor

<< Evaluation of Decomposition of Fixing Agent >> Film 3000
After processing one sheet, a fixing solution was collected and observed for the presence of cloudiness. The presence of white turbidity indicates that the fixing agent sodium thiosulfate is decomposed and sulfuration occurs.

[0136]

[Table 5]

As is clear from Table 5, according to the present invention, the residual silver and the residual color are small even at a low fixing solution temperature, and since the fixing solution temperature is low, the generation of odor is small and the fixing agent Little decomposition.

Example 4 At the time of development processing, a conveying roller (two pairs of opposing rollers) of a rack (wading rack) between a fixing tank and a washing tank of an automatic developing machine SRX-503 (manufactured by Konica Corporation) (wading roller) A transfer roller having a heater shown in FIG. 2 (using a hollow shaft 15 having an outer diameter of 24 mmφ and an inner diameter of 23 mmφ)
Was used, and the transport speed was doubled in the same manner as in Example 1, and an automatic developing machine modified to transport the film in Dry to Dry in 23 seconds was used.

The film described in Example 1 was used as the light-sensitive material. Further, the developing solution, the developing replenishing solution, and the fixing solution described in Example 1 are used as the developing solution, the developing replenishing solution, and the fixing solution.
Development processing was performed at the developer temperature and the transport roller temperature shown in Table 6.

After processing 3000 films, the residual silver, residual color and odor were evaluated in the same manner as in Example 3. Table 6 shows the obtained results.

[0141]

[Table 6]

As is clear from Table 6, according to the present invention, the residual silver and the residual color are small even at a low fixing solution temperature, and since the fixing solution temperature is low, the generation of odor is small and the fixing agent Little decomposition.

Example 5 At the time of development processing, the transport rollers arranged in a zigzag pattern on the washing rack of the automatic processor SRX-503 [manufactured by Konica Corporation] were replaced with the transport rollers having the heater shown in FIG. (Uses a hollow shaft 15 with an outer diameter of 24 mmφ and an inner diameter of 23 mmφ)
Was used, and the transport speed was doubled in the same manner as in Example 1, and an automatic developing machine modified so as to transport the film in 23 seconds in Dry to Dry was used.

The film described in Example 1 was used as the light-sensitive material. Further, the developing solution, the developing replenishing solution, and the fixing solution described in Example 1 are used as the developing solution, the developing replenishing solution, and the fixing solution.
Development processing was carried out at the washing liquid temperature and the transport roller temperature shown in Table 7. The wash water was separately temperature-controlled, and the flow rate of the wash water was 3 liters / minute.

The film prepared as described below was used as a light-sensitive material. As the developing solution, the developing replenishing solution and the fixing solution, the developing solution, the developing replenishing solution and the fixing solution prepared as described below were used, and the developing treatment was carried out at the developing solution temperature and the conveying roller temperature shown in Table 7.

With respect to the developed sample film, residual silver and residual color were evaluated in the same manner as in Example 3, and residual hypo was evaluated in the following manner. Table 7 shows the obtained results.

<< Evaluation of Residual Hypo >> The unexposed film was developed, and an aqueous solution containing 0.1 mol / liter of silver nitrate (residual hypo evaluation solution) was added dropwise to the resulting processed film, which was allowed to stand for 3 minutes. Wipe the Hypo evaluation liquid well and dry it. The concentration of the generated silver sulfide was measured by a photographic densitometer PDA-6 using a 436 ± 10 nm interference filter as a spectral filter.
5 ([Konica Corp.] is used to measure the light transmission density,
The residual hypo remaining on the film was evaluated by the difference in the light transmission density between the portion where the residual hypo evaluation liquid was dropped and the portion where the liquid was not dropped.

The larger the difference in light transmission density, the higher the residual hypo density in the film.

[0149]

[Table 7]

Since running water is used as the rinsing water, and a large amount of rinsing water is required, rinsing with rinsing water at a high temperature requires a large amount of energy and is economically large in size. It is also disadvantageous. According to the invention, Table 7
As is clear from the above, even when the temperature of the washing water is low, the residual silver, the residual color and the residual hypo are small as in the case of the temperature of the washing water being high, and the same washing effect is obtained.

[0151]

According to the present invention, even if a low temperature photographic processing solution is used, the same photographic processing as that using a high temperature photographic processing solution can be performed, and a high temperature photographic processing solution can be used. You will not suffer the disadvantages of being in

[Brief description of drawings]

FIG. 1 is an explanatory diagram for explaining an automatic processor and a photographic processing method of the present invention.

FIG. 2 is an explanatory diagram for explaining a heating / conveying roller of the present invention.

[Explanation of symbols]

 1 Development Tank 2 Fixing Tank 3 Washing Tank 4 Squeeze Section 5 Transport Roller 6 Drying Section 8 Film Inlet 9 Film Outlet 12 Roller Body 13 Electric Heater 17 Temperature Sensor

Claims (23)

[Claims] 1. A method of processing a photosensitive material in which a photosensitive material is conveyed, immersed in a processing bath, and subjected to photographic processing, a means for directly heating the photosensitive material is provided, and the photosensitive material being processed is heated. Method for processing photosensitive material. 2. The method of processing a photosensitive material according to claim 1, wherein the photosensitive material is conveyed by using a conveying roller. 3. The method of processing a light-sensitive material according to claim 1, wherein the light-sensitive material is heated by a carrying roller having a heater. 4. The method of processing a light-sensitive material according to claim 1, wherein the light-sensitive material is heated by a heating plate. 5. The method for processing a photosensitive material according to claim 1, wherein the photosensitive material is heated in a developing bath. 6. The method for processing a photosensitive material according to claim 1, wherein the heating of the photosensitive material is performed in a fixing bath. 7. The method of processing a light-sensitive material according to claim 1, wherein the light-sensitive material is heated in a washing bath. 8. The method for processing a light-sensitive material according to claim 1, wherein the light-sensitive material is heated between processing baths. 9. The method for processing a light-sensitive material according to claim 1, wherein the developing time is 4 seconds or more and 14 seconds or less. 10. The processing method according to claim 1, wherein the replenishment amount of the developing solution is 30 cc / quarter or less. 11. The method for processing a light-sensitive material according to claim 1, wherein the fixing time is 3 seconds or more and 10 seconds or less. 12. An automatic developing machine for a photosensitive material having a conveying mechanism for conveying the photosensitive material and a photoprocessing tank, wherein a means for directly heating the photosensitive material is provided between the first photoprocessing tank and the final photoprocessing tank. An automatic developing machine for photosensitive materials, which is provided. 13. The automatic developing machine for photosensitive material according to claim 12, wherein the conveying mechanism for conveying the photosensitive material is a conveying roller. 14. A roller having a heater as the means for directly heating the light-sensitive material.
Or an automatic developing machine for the light-sensitive material described in 13 above. 15. The automatic developing machine for photosensitive material according to claim 12, wherein the rollers having a heater are arranged in a zigzag pattern. 16. An automatic developing machine for photosensitive material according to claim 12, wherein the means for directly heating the photosensitive material is a heating plate. 17. A roller having a heater is provided in the photographic processing tank, and the roller is provided.
6. An automatic developing machine for a light-sensitive material according to 6. 18. The photographic processing tank provided with a roller having a heater is a developing tank.
17. An automatic developing machine for a light-sensitive material according to item 17. 19. The photographic processing tank provided with a roller having a heater is a fixing tank.
18. An automatic processor for the photosensitive material according to item 18. 20. The photographic processing tank provided with a roller having a heater is a washing tank.
19. An automatic developing machine for photosensitive material as described in 19. 21. A transport roller having a heater is provided between the photoprocessing baths.
20. An automatic developing machine for the light-sensitive material according to 20. 22. An automatic developing machine for photosensitive material according to claim 12, wherein a roller having a heater is provided between the developing tank and the fixing tank. 23. An automatic developing machine for photosensitive material according to claim 12, wherein a roller having a heater is provided between the fixing tank and the washing tank.