JP2887688B2 - Processing method using fixer for black-and-white photographic light-sensitive materials having rapid processing suitability - Google Patents

Description

The present invention relates to a processing method using a fixing solution for black-and-white photographic light-sensitive materials. More specifically, the present invention relates to a processing method using a fixing solution for a black-and-white photographic light-sensitive material capable of achieving rapid processing and improving the storage stability of a processed silver image.

[Background of the Invention]

An automatic developing machine has been developed for automatically transporting a silver halide photographic light-sensitive material after exposure, and developing, fixing, washing and, in some cases, drying (US Pat. Nos. 3,025,779 and 3,545,971). ), It has been a long time since high-temperature rapid processing became possible.

The photosensitive material for X-ray image diagnosis is processed using a roller-conveying type automatic developing machine in a total processing time of 90 seconds from when the leading end of the photosensitive material enters to when it is dried and comes out. About 20 years have passed since / P processing (90-second processing) was introduced. Under such circumstances, recently, further reduction in processing time has been desired.
Published a 45-second treatment at the North American Radiological Society in 1980, and applied for several related patents such as European Patent No. 0238271A and Japanese Patent Application Laid-Open No. 622-286037. These movements are intended to respond to urgent cases in the medical field, and are expected to accelerate in the future.

To achieve speedup, of course, the processing speed greatly depends on the developing equipment and photosensitive material, but the processing speed also depends on the processing agent. It is necessary to greatly improve various performances such as easiness. That is, even when extremely high-speed processing is performed, the fixing property is good, and there is no inconvenience due to the remaining of the fixing agent, so that the residual color of the photosensitive material after processing is small, and the storage stability of the silver image is also good. There is a long-felt need for liquids and treatment methods that have such an effect.

[Problems to be solved by the invention]

Accordingly, an object of the present invention is to provide a black-and-white photographic light-sensitive material which maintains a sufficient fixing speed even in the ultra-short processing described above, has less residual color of the light-sensitive material after processing, and further has an improved storability of silver images. An object of the present invention is to provide a processing method using a fixing solution for a material.

[Means for solving the problem]

The present inventors have conducted intensive studies and as a result, the above object of the present invention is:
Using a fixing solution for a black-and-white photographic light-sensitive material containing at least one selected from the group consisting of compounds consisting of thiosulfates, thiocyanates and inorganic halides, and having an ammonium ion content of 50 mol% or less of all cations. Have been found to be achieved by a processing method for processing a black-and-white photographic light-sensitive material by a roller transport type automatic developing machine under conditions corresponding to the following formula.

l ^0.75 × T = 50-130 0.7 <l <4.0 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the above-mentioned l.
It is the time (unit: seconds) required to pass through.

Hereinafter, the present invention will be described. The fixing solution for a black-and-white photographic light-sensitive material used in the present invention contains at least one selected from the group consisting of thiosulfates, thiocyanates, and inorganic halides, and the ammonium ion contains all cations. The fixing solution used in the present invention contains at least one selected from the group consisting of thiosulfates, thiocyanates, and inorganic halides. The amount is preferably from 0.1 to 10 mol / l, more preferably from 0.5 to 8 mol / l.
Mol / l, more preferably 0.7 to 6 mol / l,
In addition, it is preferable that ammonium ion accounts for 20 mol% or less of all cations.

In the fixing solution used in the present invention, as the thiosulfate, for example, potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate and the like are used, and these thiosulfates are preferably used at 0.5 to 2 mol / l. As the thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, lithium thiocyanate and the like are used, and these thiocyanates are preferably used at 0.7 to 3 mol / l. The halogen ion of the inorganic halide used in the fixing solution used in the present invention is limited to bromide ion and iodide ion. Therefore, as the inorganic halide, for example, hydrobromic acid,
Bromides such as lithium bromide, sodium bromide, potassium bromide, and ammonium bromide, and iodides such as sodium iodide, potassium iodide, and ammonium iodide can be used. The above compounds can be used alone or in an appropriate combination of two or more such that the ammonium ion is 50 mol% or less of all cations. When used in combination, the mixing ratio of these combinations is Optional. In addition, even if it is a halogen compound, for example, a halide by a chlorine atom or a fluorine atom does not exhibit the function and effect intended by the present invention, and thus is excluded from the present invention. When an inorganic halide is contained, as long as it contains a bromide ion or an iodine ion, the action and effect of the present invention are not affected even if these chloride ions and fluorine ions are contained together. When an inorganic bromide or iodide is used in the fixing solution used in the present invention, the content thereof is determined as follows.
1.5-3.0 mol / l for bromide, 1.
5 to 7 mol / l is preferred. In the case of using a mixture of inorganic bromide and iodide, depending on the combination amount, in total,
It is preferable to contain at least 0.5 mol / l.

The pH of the fixing solution used in the present invention is preferably 3.8 or more, particularly preferably 4.0 to 7.0.

The fixing temperature and the fixing time are preferably from about 20 ° C to about 50 ° C.
6 seconds to 90 seconds at 30 ° C, 6 seconds to 30 ° C to 40 ° C
60 seconds is more preferred. The term “fixing processing time” refers to the time during which the photosensitive material to be processed is in contact with the fixing solution. In the case of processing in an automatic developing machine, the photosensitive material is immersed in the fixing tank solution before the next washing tank solution (stabilizing solution). ) Means the time until immersion.

In the fixing solution used in the present invention, in addition to the above compounds,
Various additives such as an acid, a salt, a chelating agent, a surfactant, a wetting agent and a fixing accelerator can be contained.

Examples of the acid that can be contained include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and organic acids such as citric acid, tartaric acid, and oxalic acid.

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

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

As the surfactant, for example, anionic surfactants such as sulfates and sulfonates, nonionic surfactants such as polyethylene glycols and esters, and JP-A-57-6
And amphoteric surfactants described in JP-A-840 (name of the invention, "fixer for photography").

Examples of the wetting agent include alkanolamine and alkylene glycol.

As the fixing accelerator, for example, JP-B-45-35754,
Examples thereof include thiourea derivatives described in JP-B-58-122535 and JP-B-58-122536, alcohols having a triple bond in the molecule, and thioethers described in US Pat. No. 4,126,459.

Among the additives, acids and salts such as sulfuric acid, citric acid, and aminopolycarboxylic acids are preferable because they promote the effects of the present invention.

 A preferable addition amount of the additive is 0.5 to 20 g / l.

The fixing solution used in the present invention may further contain a hardener. Examples of the hardener include a water-soluble chromium salt and a water-soluble aluminum salt. Examples of the water-soluble chromium salt include chromium alum and examples of the water-soluble aluminum salt include aluminum sulfate, aluminum ammonium sulfate, aluminum potassium sulfate, aluminum potassium chloride, and aluminum chloride.

These hardeners are preferably used because they have a great effect on improving the strength of the film surface of the silver halide photographic material. The addition amount of the water-soluble aluminum salt is preferably
It is 0.2 to 3.0 g / l in terms of aluminum, and more preferably 1.2 to 2.5 g / l.

The constitution of the black-and-white silver halide photographic light-sensitive material applicable to the fixing solution used in the present invention is not limited, and is arbitrary. In general, a silver halide photographic material comprises a support and at least one silver halide emulsion layer coated thereon. Further, the silver halide emulsion layer can be coated not only on one side but also on both sides of the support. Of course, a back layer, an antihalation layer, an intermediate layer, an uppermost layer (for example, a protective layer) and the like can be provided as necessary.

The black-and-white photosensitive material processed by the fixing solution used in the present invention is not particularly limited in terms of other components. For example, the grain shape, structure, and the like of silver halide grains used in the photosensitive material to be processed are not limited at all. Preferably particles described in JP-A-63-23154, JP-A-58-113927, JP-A-58-113928, JP-A-59-10563
The present invention can be preferably used for photosensitive materials in which tabular graininess is used as disclosed in JP-A Nos. 6 and 60-147727.

Further, regarding emulsion and grain structure, JP-A-62-147449,
No. 62-169149, JP-A-60-136738, JP-A-60-147
No. 727, No. 60-254032, No. 60-215540, No. 61-232445
Nos. 62-3247, 62-7040, 62-54249, 62-1
23446, 62-123447, 62-124550, 62-124551
And those using the techniques disclosed in JP-A-62-124552 and JP-A-62-151840.

Regardless of the single-sided emulsion photosensitive material or the double-sided emulsion photosensitive material, the amount of silver and the amount of hydrophilic colloid of the processed photosensitive material are 1.0 to 4.5 (g / m ² ) on one side and 1.8 or less on the hydrophilic colloid.
It is preferably in the range of 4.0 to 4.0 g / m ² .

The photographic material to be processed is preferably one to which a sensitizing dye has been added between the time of silver halide grain formation and coating, and the amount of the sensitizing dye used is preferably 3 mg / m ² or more, and more preferably 5 mg / m ² or more.
~30mg / m ² is preferred.

As the sensitizing dye and the chemical sensitizing method, those described in JP-A-61-80237 are preferably used.

As other additives and means used for the photosensitive material to be processed, it is preferable to use the method described in JP-A-63-23154.

That is, the photosensitive material may contain optional additives, which are described in Research Disclosure, Vol. 176, No.
17643 (December 1978) and 187, No. 18716 (November 1976
Monthly), and the relevant locations are summarized in the following table.

Known photographic additives that can be used in the preparation of the emulsion of the light-sensitive material to be processed in the present invention are also described in the above two Research Disclosures, and the locations described in the following table are shown.

Further, as a processing agent and other processing-related technologies,
60-52848, 60-136741, and 61-36744, the technique disclosed in Mason, "Photographic Processing Chemistry" (Photographic Processing Chemis)
try), it is preferable to use the technology described in Focal Press.

Further, as the treating agent, those described on page 117, line 10 to page 123, line 12 are preferably used. Other additives include Research Disclosure No. 176, 22-31 (RD17
643, 1978) are preferably used.

Next, the processing method of the present invention will be described. In the processing method of the present invention, it is essential to use the fixing solution of the present invention. Regarding the fixing solution used in the processing method of the present invention, the above description can be applied as it is.

The photosensitive material to be processed is the same as that described in the description of the fixing solution of the present invention.

As a processing step in the processing method of the present invention, a method is preferred in which the photosensitive material is exposed, developed and fixed, then washed or stabilized, and dried.

In the practice of the present invention, the following developing agents can be used in the developing solution.

Representative of HO- (CH = CH) n-OH type developing agents include hydroquinone, and catechol, pyrogallol and derivatives thereof, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-
Examples include dibromohydroquinone and 2,5-dimethylhydroquinone.

As the HO- (CH = CH) n- NH 2 type developing agent, the ortho and para aminophenols representative and is N- methyl -p- aminophenol, also other 4-aminophenol.

Further, examples of the H ₂ N- (CH = CH) n-NH ₂ type developing agent include 4-amino-2-methyl-N, N-diethylaniline and p-phenylenediamine.

Heterocyclic developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl -4,4-dihydroxymethyl-3-pyrazolidone and the like.

The above developing agents may be used alone or in combination of two or more.

The developing agent is preferably used in an amount of usually 0.01 mol / l to 1.2 mol / l.

Preservatives preferably used in the developer include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The sulfite is preferably at least 0.1 mol / l, particularly preferably at least 0.3 mol / l. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer is preferably in the range of 9 to 13.
More preferably, the pH is in the range of 9.5 to 12.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.
Contains pH adjusters.

Buffers such as JP-A-61-28708 (borate) and JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates and carbonates may be used.

Additives used in addition to the above components include sodium bromide, potassium bromide, development inhibitors such as potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, There are organic solvents such as methanol. Also, 1-phenyl-5-
Mercaptotetrazole, a mercapto-based compound such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an indazole-based compound such as 5-nitroindazole, or a fent-inhibiting agent such as a benztriazole-based compound such as 5-methylbenztriazole. Good. Further, if necessary, a hardening agent such as formaldehyde and glutaraldehyde may be contained. It may further contain a color tone agent, a surfactant, an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244, and the like.

Silver stain inhibitors, for example, compounds described in JP-A-56-24347 can be used in the developer.

As the developer, an amine compound such as an alkanolamine described in JP-A-56-106244 can be used.

LFA Meson's "Photographic Processing Chemistry", published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

Development temperatures and times are generally preferably from about 25 ° C.
5 to 90 seconds at about 50 ° C, more preferably 8 seconds at 30 ° C to 40 ° C
Can be 1 minute.

The development processing time refers to the time during which the photosensitive material is substantially in contact with the developer, and in the case of an automatic developing machine, after the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine, It means the time until immersion in the fixing solution.

When performing water washing or stabilization treatment, as these treatments, any method known in the art can be applied, and water containing various additives known in the art is used as washing water or a stabilizing solution. It can also be used. The use of water which has been subjected to antifungal means in the washing or stabilizing solution, a photosensitive water-saving processing of the material 1 m ² per 3l less replenishing amount not possible to become only further stock pipe for installation of an automatic processor is not required Tanks can be reduced.

When washing with a small amount of washing water, it is more preferable to provide a squeeze roller washing tank described in JP-A-62-32460.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with antifungal water according to the treatment, is disclosed in
As described in JP-A-60-235113, it can also be used for a processing solution having a fixing ability which is a preprocessing step.

Furthermore, antibacterial agents, anti-binder agents, surfactants and the like described in JP-A-57-8542 and the like can also be used in combination.

Furthermore, in the washing bath, RTKreiman's J. Image, Tech 10.
(6) The isothiazoline compounds described in 242 (1984) and the like, the compounds described in Japanese Patent Application No. 61-51396, and the like can be used in combination as a microbiocide.

The water stored in the water stock tank with the antifungal means is preferably used as both a diluting water for the undiluted processing solution such as the developer and the fixing solution and a washing water, since the space can be reduced. However, the diluted water and the washing water (or stabilizing solution) provided with the antifungal means can be separately stored in separate tanks, or only one of them can be taken directly from the tap water.

When stored separately in separate tanks, various additives can be added to the washing water (or stabilizing bath), for example, in addition to the antifungal means.

For example, the chelate stability logK value with aluminum is
Ten or more chelate compounds may be contained. These are effective for preventing white precipitation in the washing water when the fixing solution contains an aluminum compound as a hardener.

Specific examples of the chelating agent include ethylenediaminetetraacetic acid (logK16.1) and cyclohexanediaminetetraacetic acid (1
7.6), diaminopropanoltetraacetic acid (13.8), diethylenetriaminepentaacetic acid (18.4), triethylenetetraminehexaacetic acid (19.7) and the like, and their sodium salts, potassium salts, and ammonium salts. 1010 g / l, more preferably 0.1-5 g / l.

Further, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of a cationic type, an anionic type, a nonionic type and a zwitterionic type may be used. Specific examples of the surfactant include, for example, compounds described in “Surfactant Handbook” issued by Kogyo Tosho Co., Ltd.

Various compounds may be added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg, pH
3-8) for various buffers (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) And aldehydes such as formalin as typical examples. In addition, various additives such as a chelating agent, a bactericide (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), a surfactant, an optical brightener, a hardener, and the like may be used. The same or different target compounds may be used in combination of two or more. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storability.

Washing or stabilizing bath temperature and time by the above method,
6 seconds to 90 seconds at 0 ° C to 50 ° C are preferred.

The rinsing (stabilization) processing time is the time during which the photosensitive material to be processed is immersed in rinsing water (or a stabilizing solution). It is the time of immersion.

In practicing the present invention, the photographic light-sensitive material which has been developed, fixed and washed or stabilized is preferably squeezed with washing water or a stabilizing solution, that is, dried through a squeeze roller method. The drying in this case is generally performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but is usually about 5 seconds to 90 seconds, more preferably 40 ° C. to 90 ° C.
About 5 to 60 seconds at 80 ° C.

Next, conditions for processing by a roller transport type automatic developing machine according to the processing method of the present invention will be described.

L (unit: m), which is the processing length (the length from the core of the first roller at the insertion port of the automatic developing machine to the core of the final roller at the drying outlet) when processing the photosensitive material, is sensitivity, transport sex,
0.7 <l <4.0 from the viewpoint of the film being easily scratched. The product of l ^0.75 and T (the time (unit: seconds) required for the photosensitive material to pass through l) is 50 to 130 from the viewpoint of sensitivity, color remaining, image graininess, and fog. .
Preferably it is 76 or more.

The above 1 can be obtained, for example, by measuring a photosensitive material using a polyethylene terephthalate support having a thickness of 180 μm as a reference.

According to the above-mentioned processing conditions, good results can be obtained in which the granularity is good while having high sensitivity, and in which poor fixing, poor washing, and poor drying hardly occur.

In the processing method of the present invention, the number of all the transport rollers is a value obtained by dividing the processing length l by the number of rollers is 0.01 to
Preferably, it is in the range of 0.04. The time of each processing part is preferably in the following range.

Inserting + developing + migratory 25-40% Fixing + migratory 12-25% Washing + migratory 10-25% squeeze + drying 25-45% total 100% The roller used is 12mm-60mm in diameter of the conveying part,
The length is preferably between 30 cm and 110 cm, and various materials can be used. For example, bakelite-based materials (which may include glass powder, metal powder, and plastic powder) in the areas of development, fixing, washing, and drying are used. And rubber (neoprene, isoprene, silicone rubber, etc.). It is preferable to use water-repellent and elastic silicon rubber or the like, or "Kurarino" (trade name, a product of Kuraray Co., Ltd.), a synthetic leather having high water absorption, for the transition portion and the squeeze portion.

〔Example〕

Hereinafter, embodiments of the present invention will be described in detail. However, needless to say, the present invention is not limited to the embodiments described below.

Example-1 (Preparation of film) 2.0 mol% of silver iodide having an average grain size of 0.28 μm by a double jet method, while controlling at 60 ° C., pAg = 8.0 and pH = 2.0.
A monodispersed cubic silver iodobromide emulsion containing

Then, a part of this emulsion was used as a core and grown as follows. That is, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added to the solution containing the core particles and gelatin at 40 ° C., pAg 9.0 and pH 9.0 by a double jet method, and silver iodide was added in an amount of 30 mol. % Of the first coating layer. Further, an ammonium silver nitrate solution and a potassium bromide solution were further added by a double jet method at pAg = 9.0 and pH = 9.0 to form a second coating layer, and a cubic monodisperse iodobromide having an average particle diameter of 0.63 μm was formed. A silver emulsion was prepared.

After removing excess salts by the coagulation sedimentation method, chloroaurate 8 × 10 ^-7 mol, sodium thiosulfate 7 × 10 ^-6 mol, ammonium thiocyanate 7 × 10 ^-4 mol per mol of silver halide.
And sensitizing dyes (A) and (B) described below and potassium iodide at 1 × 10 ^-3 mol / l.
Molar AgX was added and optimally spectrally sensitized (AgX indicates silver halide; the same applies herein).

After completion of the spectral sensitization, silver halide 1
Per mole, In addition, a coating solution for an emulsion layer was prepared.

In addition, the following compounds were added as protective layer additives to prepare a protective film layer coating solution. That is, per 1g of gelatin, And so on.

The above-mentioned emulsion layer coating solution was coated with this protective film layer coating solution on both sides of a 180 μm-thick undercoated blue-colored polyethylene terephthalate support by a slide hopper coating machine, and the silver amount was 2.4 g / side on one side. m ² , gelatin on one side 3.8
g / m ² to obtain a film 1 which is a sample of the photosensitive material to be processed.

Next, in water 1, gelatin 30g, potassium bromide 10.5
g, and 8 ml of a 0.5 wt% aqueous solution of the following thioether [HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH] was added and dissolved, and the solution was kept at 65 ° C. While stirring (pAg = 8.5, pH = 6.5), 30 ml of a 0.88 mol silver nitrate solution and 30 ml of a mixed solution of 0.88 mol of potassium iodide and potassium bromide (molar ratio 96.5: 3.5) were simultaneously stirred for 15 seconds while stirring. After the addition, 600 ml of a 1 mol silver nitrate solution and 600 ml of a 1 mol mixed solution of potassium bromide and potassium iodide in a molar ratio of 96.5: 3.5 were added simultaneously over 70 minutes,
Average grain size 1.18μm, thickness 0.26μm, silver iodide content
A 3.5 mol% tabular silver iodobromide emulsion was prepared.

Then, after removing excess salts by the coagulation sedimentation method, these emulsions were treated in the same manner as in the above-mentioned film 1 to obtain a film 2.

(Preparation of Fixing Solution) As shown in Table 1 below, seven types of fixing solutions were prepared. All fixers were adjusted to 1 with water. However, the pH was adjusted to 4.80 with acetic acid.

(Film processing and evaluation) XD-SR was used as a developing solution using the automatic developing machine shown in FIG.
(Konica Corporation), and the above-mentioned films 1 and 2 were treated using fixing solutions shown in Table-2.

 The processing time T was 46 seconds, and the processing length 1 was 2.74 m.

In FIG. 1, 1 is a first roller at a photosensitive material insertion opening, 2 is a final roller at a drying outlet, 3a is a developing tank, 3b is a fixing tank, 3c.
Denotes a washing tank, 4 denotes a photosensitive material to be processed, 5 denotes a squeezing section, 6 denotes a drying section, and 7 denotes a dry air outlet.

 The processing conditions were set as follows.

Temperature Replenishment amount Developing 35 ℃ 33cc / quarter 1 fixation 33 ℃ 63cc / quarter 1 water washing 20 ℃ set to 1.5l / min Drying 45 ℃ Each of the processed films was evaluated for the following two items.

(1) Residual Color The unexposed sample was passed through an automatic developing machine for each film, and the resulting film was visually evaluated for residual color. The evaluation was performed in the following five-step evaluation.

1: No residual color 2: Slight residual color, but good 3: Remaining color, but no problem in use 4: Remaining color, unusable 5: Severe residual color, unusable (2) Evaluation of silver image storability Films 1 and 2 each having a size of 30 cm × 30 cm were uniformly exposed to a transmission light blackening density of 1.0, and developed under the conditions shown in Table 2 to obtain a silver tone on a Schaukasten. Was visually evaluated. The evaluation was performed in the following four grades.

A: Black B: Slightly reddish black C: Slightly yellow-red black D: Yellow-reddish black
, And visually evaluated for the silver tone after 3 days.

 Table 2 shows the obtained results.

As is evident from Table 2, the fixing solution used in the present invention has no deterioration in the fixing ability, and according to the processing method according to the present invention using the fixing solution, the residual color of the obtained image is of no problem. It can be seen that the silver tone was good on the same day, the silver tone was hardly degraded even after storage, and the storage stability was good.

As is evident from Table 2, the processing method of the present invention using the fixing solution used in the present invention gives an image having excellent residual color properties and silver image preservability.

Example 2 As the developing solution and the fixing solution, those prepared in Example 1 were used, and the processing time was changed by the automatic developing machine used in Example 1 as shown in Table-3. did. In addition, the film 1 was used for the sample to be processed.

In the same manner as in Example 1, residual colorability and storage stability of the silver image were evaluated.

Further, using a screen KO-250 manufactured by Konica Corporation, relative sensitivity was set to 100, where the reciprocal of the X-ray dose giving a blackening density of fog +1.0 in Experiment No. 15 in Table 3 was set to 100, and the fog value was calculated. .

Further, the same evaluation was performed on the automatic developing machine shown in FIG. 2 while changing the processing time.

As is evident from Table 3, the processing method of the present invention treated with the fixing solution used in the present invention can provide an image having excellent residual color and silver image preservability.

[Effects of the Invention] As described above, according to the present invention, a sufficient fixing speed can be maintained even when an ultra-short processing, which is an extremely high-speed processing, is performed, and the residual color of the image of the processed photosensitive material is maintained. And the storage stability of the silver image is good.

[Brief description of the drawings]

FIG. 1 and FIG. 2 are configuration diagrams of an automatic developing machine used in an embodiment of the present invention. 1 ... roller, 2 ... final roller at the drying outlet, 3a ...
Developing tank 3b Fixing tank 3c Rinse tank 4 Photosensitive material 5 Squeeze section 6 Drying section 7 Dry air outlet.

Claims (1)

(57) [Claims] 1. A roller type automatic processor under the conditions corresponding to the following formula, containing at least one compound selected from the group consisting of thiosulfates, thiocyanates and inorganic halides, and ammonium A processing method for processing a black-and-white photographic light-sensitive material using a fixing solution in which ions are 50 mol% or less of all cations. l ^0.75 × T = 50-130 0.7 <l <4.0 where l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the above-mentioned l.
It is the time (unit: seconds) required to pass through.