JPH03269423A - Processing method for silver halide photographic sensitive material for black and white - Google Patents

Abstract

PURPOSE:To allow the high-speed processing of the above photosensitive material and to eliminate ammonia smells and the deterioration in fixing power by using a fixer having a specific value or above of the concn. of potassium ions. CONSTITUTION:The silver halide photosensitive material for black and white is processed by the fixer of >=0.5g ion/l concn. of the potassium ions. Thiosulfate (e.g.: potassium potassium) and/or halogen compd. (e.g.: potassium bromide) are preferably incorporated into this fixer and further, the thiosulfate (e.g.: sodium thiosulfate), water-soluble aluminum salt (e.g.: aluminum sulfate), desired org. acid (salt) (e.g.: citric salt), preservative (e.g.: sulfate), etc., may be added to the fixer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for processing black and white silver halide photographic materials, and particularly to a fixer solution for black and white silver halide photographic materials (hereinafter referred to as (sometimes simply referred to as a fixer).

[Conventional technology]

It is well known that a fixing process is performed after developing a black and white silver halide photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material). For example, it is known to fix with fixers containing thiosulfate, and furthermore to fix with fixers containing sulfite to prevent decomposition of the thiosulfate. It is also known and widely used to include a water-soluble aluminum compound in a fixer solution in order to harden the film surface of a photosensitive material.

In recent years, large quantities of photosensitive materials have come to be processed by automatic processing apparatuses, and there has been a desire to shorten the processing time. Therefore, it is desired to shorten the fixing time as well. Therefore, in order to increase the fixing speed, the concentration of thiosulfate is on the rise.

As for the type of thiosulfate to be contained in the fixing solution, ammonium salts are often used because of their high fixing speed.

However, when ammonium salts such as ammonium thiosulfate are used in the fixer and the film, which is the photosensitive material to be processed, is directly fed into the fixer tank without going through the process of returning after development, for example, a large amount of When processed continuously,
Ammonia gas is likely to be generated due to pH fluctuation (increase) in the fixer caused by the developer brought into the fixer tank by the film. This is also unfavorable in terms of the working environment, for example, when developing processing is performed in a narrow room.

Generally, sensitizing dyes and various dyes are sometimes added to photosensitive materials in order to improve their performance, such as increasing their sensitivity. If this happens, the decolorization properties of these pigments and dyes and their elution into the processing solution will decrease, causing problems such as uneven color staining (deterioration of residual color) in the resulting silver image. arise.

[Purpose of the invention]

A first object of the present invention is to solve the above-mentioned problems and provide a processing method for black-and-white silver halide photographic light-sensitive materials that is capable of high-speed processing and is favorable in terms of working environment. A second object of the present invention is to enable high-speed processing, without causing fluctuations in photographic performance, deterioration of fixing ability, and especially deterioration of residual color of photosensitive materials to be processed, and which is favorable in terms of the working environment. An object of the present invention is to provide a method for processing a certain silver halide photographic material.

[Structure and operation of the invention]

The above object of the present invention is to produce a black and white silver halide photographic light-sensitive material with a potassium ion concentration of 0.5 gram ion/1.
This has been achieved by the method for processing a black and white silver halide photographic material, which is characterized by processing with the fixer as described above.

In the present invention, it is a preferred embodiment that the fixing solution contains a thiosulfate and/or a halogen compound.

Further, one preferable embodiment is that the processing is performed using a roller conveyance type automatic developing machine under conditions corresponding to the following formula.

1 '-'' The material is above
This is the time required to pass through (unit: 2 seconds).

The present invention will be explained in more detail below.

The processing method of the present invention is for processing a black and white silver halide photographic light-sensitive material. First, the photosensitive material to be processed in the present invention will be described.

The structure of the black-and-white photosensitive material processed according to the present invention is not particularly limited. For example, the grain shape and structure of the silver halide grains used in the photosensitive material to be processed are not limited in any way.

Preferably, the particles described in JP-A No. 63-23154,
The present invention is preferably applied to photosensitive materials in which tabular graininess is used as disclosed in JP-A-58-113927, JP-A-5B-113928, JP-A-59-105636, and JP-A-60-147727. I can do it.

Furthermore, regarding emulsion and grain structure, JP-A-62-14744
No. 9, No. 62-169149, and JP-A No. 1983-
No. 136738, No. 60-147727, No. 60-2
No. 54032, No. 60-215540, No. 61-23
No. 2445, No. 62-3247, No. 62-7040, No. 62-54249, No. 62-123446, No. 62-123447, No. 62-124550, No. 6
No. 2-124551, No. 62-124552, No. 62
It is preferable to use the technique disclosed in Japanese Patent No.-151840.

The amount of silver and the amount of hydrophilic colloid in the photosensitive material to be processed, regardless of whether it is a single-sided emulsion photosensitive material or a double-sided emulsion photosensitive material, is 1.0 to 4.5 (g/rrf) on one side, and the amount of hydrophilic colloid on one side is 1.0 to 4.5 (g/rrf). It is preferable that the amount is in the range of 1.8 to 4.0 (g/nf).

The photosensitive material to be processed is preferably one to which a sensitizing dye is added between the time of silver halide grain formation and the coating, and the amount of the sensitizing dye used is preferably 3 g/rrr or more, particularly 5 to 30 g/rrr. /rd is preferred.

As a sensitizing dye and chemical sensitization method, JP-A-61-802
It is preferable to use the one described in Publication No. 37.

In addition, it is preferable to use the method described in JP-A No. 63-23154 as additives and means used in the photosensitive material to be processed.

That is, the photosensitive material may contain arbitrary additives, and these are described in Research Disclosure Vol. 176, N.
o, 17643 (December 1978) and Vol. 187, Hiroshi 18716 (November 1976), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in preparing the emulsion of the photosensitive material to be processed in the present invention are also based on the above two research studies.
The information is listed in the disclosure, and the locations are shown in the table below.

In addition, as for processing agents and other processing-related technologies,
No. 0-52848, No. 60-136741, No. 61-
36744, and "Photographic Processing Chemistry" by Mason (Ph.

tographic Processing Chem
istry), Focal Press (Focal Pr
It is preferable to use the technique described in ESS) Publishing.

Further, as the processing agent, it is preferable to use those described from page 117, line 1o to page 123, line 12. Other additives include Research Disclosure No. 176,
22-31 (RD 17643.1978) is preferably used.

Next, the fixing solution used in the processing method of the present invention has a potassium ion concentration of 0.5 g ion/l or more.

In order to provide potassium ions to the fixer used in the present invention, a water-soluble potassium salt may be added to the fixer. For example, potassium salts that can also function as fixing agents can be used, such as potassium thiosulfate, potassium thiocyanate, potassium bromide, and potassium iodide.

The fixer used in the present invention has a potassium ion concentration of 0.5 gram ion/l or more as described above, but also has a potassium ion concentration of 1.0 gram ion/1 or more and 6.0 gram ion/l or less. It is preferable that there be.

The above-mentioned potassium salt can function as a fixing agent that reacts with silver halide to form a water-soluble complex salt, which is used in ordinary fixing processing, but in the fixing solution used in the present invention, Other fixing agents may optionally be included. For example, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate, bromides such as lithium bromide and sodium bromide, halogen compounds such as iodides such as sodium iodide, or thiourea,
Typical examples include thioether. These representative fixing agents can be used alone or in an appropriate combination of two or more, and when used in combination, the mixing ratio of the combination is arbitrary. The ratio to potassium ions is also arbitrary.

In the present invention, it is preferable to use thiosulfate or a halogen compound alone or in combination as the fixing agent.

As the thiosulfate, sodium salts and potassium salts are preferred, and potassium salts are particularly preferred. Further, as the halogen compound, iodide, particularly potassium iodide is preferable.

The amount of the fixing agent used can be varied as appropriate, and the preferred amount is generally about 0.1 to about 6 mol/i! , is.

The fixer may contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potash alum, and the like.

In the fixing solution used in the present invention, tartaric acid, citric acid, malic acid, succinic acid or derivatives thereof, 75-nopolycarboxylic acid, aminopolyphosphonic acid or a salt thereof may be used alone or in combination of two or more. preferable. When using these compounds, the effects of the present invention can be further enhanced by adding 0.004 mol or more per fixer 11.

Specifically, citric acid, isocitric acid, malic acid, succinic acid, and optical isomers thereof can be used.

Also, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, lithium tartrate,
Potassium tartrate, sodium tartrate, potassium sodium tartrate, lithium hydrogen tartrate, lithium potassium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, ammonium hydrogen tartrate, magnesium hydrogen tartrate, potassium boron tartrate, ammonium tartrate, potassium ammonium tartrate, potassium aluminum tartrate, tartaric acid antimonyl potassium, antimonyl sodium tartrate,
Lithium, potassium, sodium, ammonium salts, etc. represented by sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc. can be used. Further, as specific examples of aminopolycarboxylic acid and aminopolyphosphonic acid, JP-A-63-18
A-1 to A-1 on page 10 of Publication No. 2650
Compounds such as No. 2 can be used.

Preservatives (sulfite, bisulfite) may be added to the fixer if desired.
, pH buffer (acetic acid, nitric acid), pH 1! Conditioners (eg sulfuric acid), water softening capable chelating agents may be included. The amount of preservative used can be varied as appropriate, and is preferably about 0.05 to 1 mol/l. The pH of the fixer is 3.
8 or more is preferable, and 4.0 to 5.5 is particularly preferable.

The fixing temperature and time are generally preferably about 20°C to about 5°C.
It can be carried out at 0°C for 6 seconds to 90 seconds, and at 30°C to 40°C.
6 seconds to 60 seconds is more preferable. Note that the fixing processing time refers to the time during which the photosensitive material is in contact with the fixing solution, and in the case of automatic processor processing, after the photosensitive material to be processed is immersed in the fixing tank solution, the next washing tank solution ( This refers to the time required for immersion in a stabilizing solution.

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

Examples of developing agents that can be used in the developer when carrying out the present invention include the following.

Typical examples of HO-(CH=CH) n-OH type developing agents include hydroquinone, as well as catechol, 1:"o-cal and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, Isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2゜5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Examples include 2,5-dimethylhydroquinone.

Typical examples include IO-(CH=CH)n-NHz type developing agents, ortho and rose aminophenols, N-methyl-p-aminophenol, and other 4-
There are also aminophenols.

Examples of the HzN-(CH=CH)n-NHz type developing agent include 4-amino-2-methyl-N, N-diethylaniline, and p-phenylenediamine.

Heterotypical developing agents include l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-3-pyrazolidone. Examples include 4,4-dihydroxymethyl-3=pyrazolidone.

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, and sodium formaldehyde bisulfite. The amount of sulfite is preferably 0.1 mol/1 or more, particularly 0.3 mol/1 or more. Further, the upper limit is preferably 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 pH include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-609
No. 3439 (e.g. sucrose, acetoxime, 5
Buffers such as -sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, There are organic solvents such as methanol. In addition, mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole. It may contain antifoggants such as, and further may contain hardeners such as formaldehyde and glutaraldehyde, if necessary. Furthermore, it may also contain a toning agent, a surfactant, an antifoaming agent, a water softener, an amine compound described in JP-A-56-106244, and the like.

Silver stain inhibitors, such as the compounds described in JP-A-56-7, can be used in the developer.

As the developer, amine compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2.19.
3.

015, 2,592.364, and JP-A-48-6 may be used.

The processing temperature and time are generally preferably about 25°C.
~5 to 90 seconds at about 50''C, more preferably 30゛C~
It can be heated at 40°C for 8 seconds to 1 minute.

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 processor, the time from when the photosensitive material to be processed is immersed in the developer tank solution of the automatic processor to the next time. Refers to the time required to immerse in fixer.

When carrying out water washing or stabilization treatment, any method known in the art can be applied for these treatments, and water containing various additives known in the art can be used as the washing water or stabilizing liquid. It can also be used. 31 per rrf of photosensitive material by using anti-mildew water for washing or stabilizing solution! Not only is it possible to save water by replenishing the amount below, but it also eliminates the need for piping for installing an automatic developing machine, making it possible to further reduce the number of stock tanks.

When washing with a small amount of water, use JP-A-62-3246.
It is more preferable to provide the squeeze roller cleaning tank described in No. 0.

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 water treated with anti-mold means, according to the treatment, is
As described in Japanese Patent No. 0-235113, it can also be used in a processing liquid having a fixing ability, which is a pre-processing step.

Furthermore, antibacterial agents, anti-inflammatory agents, surfactants, etc. can also be used in combination.

Furthermore, for the water washing bath, R.T. Kreisan, J.Im.
age+Tech 10. (6) Isothiazoline compounds described in 242 (1984) etc., patent application No. 1983-5
The compounds described in No. 1396 are used as antibacterial agents (Micr
It can also be used in combination as (obiocide).

It is preferable that the water treated with anti-mildew means and stored in the water stock tank be used both as dilution water for the undiluted solution of the processing solution such as the developer and fixer, and also as washing water, since it takes up less space. However, it is also possible to separate the dilution water treated with anti-mold and the rinsing water (or stabilizing liquid) and store them in separate tanks, or to take only one of them directly from the tap.

When stored separately in separate tanks, the washing water (or stabilizing bath) may contain various additives in addition to being treated with anti-mold measures, for example.

For example, a chelate compound having a log K value of chelate stability with aluminum of 10 or more may be included. These are effective in preventing scuttling in washing water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (log K16.1), cyclohexanediaminetetraacetic acid (log K17.6), diaminopropanol tetranodic acid (log K13.8), and diethylenetriamine pentanolytic acid (log K18.4).
) Triethylenetetraminehexaacetic acid (19.7), etc., and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01 to 10g/It.
, more preferably 0.1 to 5 g/It.

Furthermore, in addition to the silver image stabilizer, various surfactants may be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of the cationic type, negative ionic type, nonionic type, and amphoteric type may be used. Specific examples of surfactants are listed in the "Surfactant Handbook" published by Kogaku Tosho ■. There are compounds listed.

Various compounds may be added to the stabilizing bath for the purpose of stabilizing the image.For example, adjusting the membrane pH (for example, p
H3-8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as formalin (used in combination with acids, etc.) and formalin. In addition, chelating agents, fungicides (thiazole,
Various additives such as isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents may be used.
Two or more compounds for the same or different purposes may be used in combination, and it is recommended to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate to improve image storage stability. It is preferable to

The water washing or stabilization bath temperature and time according to the above method are 0.
C. to 50.degree. C. and preferably 6 seconds to 90 seconds.

Washing (stabilization) processing time refers to the time during which the photosensitive material to be processed is immersed in washing water (or stabilizing liquid). This is the soaking time.

When carrying out the invention, the developed, fixed and washed or stabilized photographic material is preferably dried by squeezing out the washing water or stabilizing liquid, i.e. via a squeeze roller method, in which case drying is generally Drying is carried out at about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 90 seconds, more preferably 40°C.
~80''C for about 5 seconds to 60 seconds.

Next, preferred conditions when the processing method of the present invention uses a roller conveyance type automatic developing machine will be described.

1 (unit: 2 m), which is the processing section (length from the core of the 10th roller at the insertion port of the automatic processor to the core of the final roller at the drying outlet) when processing photosensitive materials, is determined by the sensitivity, conveyance, etc. In terms of quality and ease of scratches on the film, 0.7 < 41!
<4.0 is preferable, and Io・7S and T (time required for the above photosensitive material to pass through the above 1 (unit: 2 seconds))
The product is preferably 50 to 130, more preferably 76 or more, from the viewpoint of sensitivity, color residue, image graininess, and fog.

Note that the above l can be obtained by measuring, for example, a photosensitive material using a polyethylene terephthalate support having a thickness of 180 am.

According to the above processing conditions, it is possible to obtain good results that have high sensitivity, good graininess, and are less prone to poor fixing, poor washing, and poor drying.

When processing using an automatic developing machine, it is preferable to use a roller transport type automatic developing machine as described above, and in that case, the total number of transport rollers is 0. It is preferable that it be in the range of 0.01 to 0.04. Further, the time for each treatment site is preferably within the following range.

Insertion + development 25-40% Fixing + transfer 12-25% Washing + transfer 10-25% Squeeze + drying 25-45% Total 100% The rollers used have a transport section with a diameter of 12 mm - 60 mm.
mm, the length is preferably between 30C111 and 110cIIO, and various materials can be used, such as developing, fixing,
Bakelite-based materials (which may contain glass powder, metal powder, plastic powder, etc.) or rubber-based materials (neobrene, isoprene, silicone rubber, etc.) can be used for the washing and drying parts. For the transition part and the squeeze part, it is preferable to use water-repellent and elastic silicone rubber or the like, or highly water-absorbent synthetic leather brand name "Clarino" (manufactured by Kuraray ■).

〔Example〕

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

Example-1 (Preparation of film) While controlling at 60°C, pAg = 8.0, pH = 2.0, the average particle size was 0.28 μm using the double jet method.
A silver iodobromide monodispersed cubic emulsion containing 2.0 mol % of silver iodide was obtained.

Then, a part of this emulsion was used as a core and grown as follows. That is, to a solution containing the core particles and gelatin at 40° C., p A g 9.0, pH 9, OT: an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added by a double jet method to obtain silver iodide. A first coating layer containing 30 mol % of And further pAg=
9.0, pH = 9.0, ammoniacal silver nitrate solution and potassium bromide solution were added by double jet method to form a second coating layer, and a cubic crystal monodisperse iodine with an average particle size of 0.63 μm was formed. A silver oxide emulsion was prepared.

After removing excess salt by coagulation precipitation method, silver halide 1
Per mole chlorauric acid 8X10-' mol, sodium thiosulfate 7X10-' mol, ammonium thiocyanate 7
Add 10-' mol of X to perform optimal gold/sulfur sensitization, and then add the following sensitizing dyes (A) and (B) and 1X potassium iodide.
Optimum spectral sensitization was achieved by adding 10-'' mol of AgX (AgX represents silver halide, the same herein).

Sensitizing dye (A) Sensitizing dye (B) (shifi 4) υ36a (L, tl t) 4) υ3 After spectral sensitization, lime treatment is used as an emulsion layer additive per mole of silver halide. Ossein gelatin 90 g, t-butyl-catechol 400 [.

4-hydroxy-6-methyl-1°3.3a, 3 g of 7-chitrazaindene, 1.0 g of polyvinylpyrrolidone (molecular weight 10.000).

Styrene-maleic anhydride copolymer 2.5 g, trimethylolpropane 10 g, diethylene glycol 5 g.

Nitrophenyl-triphenylphosphonium chloride 50■, 1.3-dihydroxybenzene-4-ammonium sulfonate 4g12-Mercaptobenzimidazole-5-sodium sulfonate 15■, 1.1-dimethylol-1-bromo-1- An emulsion layer coating solution was prepared by adding 10 μm of nitromethane.

In addition, the following compounds were added as protective layer additives to prepare a protective layer coating solution. That is, C4F per gram of gelatin? 5O3K 3
■, CJ r *0 (CHtCHzO) r. CHtC
HtOH5■, sodium chloride
3■, (n is a mixture of 2 to 5) bisvinylsulfonyl methyl ether lO■, a matting agent made from polymethyl methacrylate with an average particle size of 5 μm 7■, an average particle size of 0
．． 11 g of colloidal silica with a diameter of 0.013 μm was added.

The above-mentioned emulsion layer coating solution and this protective layer coating solution were coated on both sides of a 180 μm thick undercoated blue colored polyethylene terephthalate support using a slide hopper coating machine, with a silver content of 2.4 g per side. 3.8 g of ceratin was applied to one side of the film to obtain Film 1, which was a sample of the photosensitive material to be processed.

Next, in 11 parts of water, 30 g of gelatin, 10 parts of potassium bromide
．． 5 g, and the following thioether [HO(CHz) z
s(Cut) ts(CHz) *5(CHz) *O
Add 8d of a 0.5 wt% aqueous solution of H] to dissolve, and heat at 65°C.
(p A g = 8.5, pH = 6
．． 5), add 0.88 molar silver nitrate solution 30 molar with stirring.
M! , and a mixed solution of 0.88 mol of potassium iodide and potassium bromide (molar ratio 96.5:3.5) 30 m for 15 seconds T! After simultaneous addition, a 1 mol silver nitrate solution 6001d and a 1 mol mixed solution 6 consisting of potassium bromide and potassium iodide in a molar ratio of 96.5:3.5 were added.
001d was simultaneously added over 70 minutes, and the average particle size was 1.1.
8μm, thickness 0.26μm, silver iodide content 3.5
A mol % tabular silver iodobromide emulsion was prepared.

After removing excess salt by a coagulation-sedimentation method, these emulsions were treated in the same manner as for Film 1 to obtain Film 2.

(Running processing test) Using the automatic developing machine shown in Figure 1, XD-3 was used as the developing solution.
Using R (manufactured by Konica Corporation) and the fixing solution shown in Table 2, the above-mentioned films 1 and 2 were subjected to running treatment.

The processing time T = 46 seconds and the processing length 12 = 2.74 m.

In FIG. 1, 1 is the 10th roller at the photosensitive material insertion port, 2 is the final roller at the drying outlet, 3a is the developing tank, 3b is the fixing tank, 3
C is a washing tank, 4 is a photosensitive material to be processed, 5 is a squeeze section, 6 is a drying section, and 7 is a drying air outlet.

The processing conditions were set as follows.

Temperature Replenishment amount Development 35°C 33cc/1 sheet cut into 4 pieces Fixing 33°C 63 cc/1 sheet cut in 4 pieces Water Washing 2
0℃ 1. FM! /win Setting Drying: 45°C (Preparation of Fixer) Four types of fixers were prepared as shown in Table 1 below. All fixers are 11 with water! ,. However, the pH should be adjusted to 4 with acetic acid.
．． It was set at 80.

Table (Treatment and Evaluation) Running treatment was performed as follows. That is, Film 1 and Film 2 were each exposed to a density of 1.2, and 1000 sheets of four-cut size were continuously processed.

The following three items were evaluated.

(1) Ammonia odor The state of ammonia odor generation was evaluated at the Oth, 500th, and 1000th sheets of the running process.

The evaluation criteria were as follows.

○: Ammonia odor is not very strong △: Ammonia odor is slightly observed: Ammonia odor is observed × (2) Color retention For each film, at the end of the run, pass the unexposed sample through and check the residual color. This was used as a sample for color evaluation. The resulting film was visually evaluated for residual color. The evaluation was made on a five-level scale as shown below.

1: No residual color 2: Good although there is a slight residual color 3: There is residual color but no problem in use 4: There is residual color and it cannot be used 5: There is a lot of residual color and it cannot be used (3) Residual silver before and after running for each film (0th, 10th
00th sheet), and an unexposed sample was used as a sample for residual silver evaluation. One drop of a 2.6 x 10-3 mol/l aqueous solution of sodium sulfide as a residual silver evaluation solution was dropped onto the above sample for residual silver evaluation, and after standing for 3 minutes, the remaining solution was wiped off and the solution was heated at room temperature.
It was left at room temperature for 15 hours. Then, using a PDA-65 density needle (manufactured by Konica Corporation), measure the transmission density of blue light in the area where the residual silver evaluation solution was dropped and the area where it was not dropped, and the difference (dropped area - undropped area). ) was used as a measure of residual silver. The greater this difference, the higher the residual silver concentration in the film after processing.

The results obtained are shown in Table-2.

As is clear from Table 2, the fixer according to the present invention has no deterioration in fixing ability, suppresses the generation of ammonia odor, and is favorable in terms of the working environment.

Example 2 The developer and fixer prepared in Example 1 were used, and the processing time was varied as shown in Table 3 using the automatic developing machine used in Example 1. I let it happen and processed it. Film 1 was used as the sample to be processed.

Running treatment was performed in the same manner as in Example 1, and ammonia odor, residual color, and residual silver were evaluated.

In addition, relative sensitivity and fog values were determined using a screen KO-250 manufactured by Konica Corporation, with the reciprocal of the X-ray dose giving a fog of 9 + blackening density of 1.0 in the experiment shown in Table 3 as 100.

Furthermore, the same evaluation was conducted using the automatic developing machine shown in FIG. 2 while varying the processing time.

The results are shown in Table-3.

As is clear from Table 3, when processing with the fixing solution according to the present invention, no ammonia odor is generated, and when compared under the same processing conditions, processing with significantly less fog and deterioration of fixing performance can be achieved.

〔Effect of the invention〕

As mentioned above, the processing method of the present invention is a processing method that allows high-speed processing, is preferable in terms of the working environment, and does not cause fluctuations in photographic performance, deterioration of fixing ability, and especially deterioration of residual color of the photosensitive material to be processed. It has the effect of never happening.

[Brief explanation of drawings]

FIGS. 1 and 2 are configuration diagrams of an automatic copying machine used in an embodiment of the present invention. l...Roller, 2...Final roller 3 at the drying outlet
a...Developing tank, 3b...Fixing tank, 3C...Washing tank, 4...Photosensitive material, 5...Squeezing section, 6...Drying section, 7...Dry air blowing Exit.

Claims (1)

[Scope of Claims] 1. A black and white silver halide photographic material characterized in that a black and white silver halide photographic light-sensitive material is processed with a fixing solution having a potassium ion concentration of 0.5 gram ions/l or more. How to process photosensitive materials. 2. The method for processing a black and white silver halide photographic material according to claim 1, wherein the fixing solution contains a thiosulfate and/or a halogen compound. 3. The method for processing a black and white silver halide photographic light-sensitive material according to claim 1 or 2, wherein the processing is carried out using a roller conveyance type automatic developing machine under conditions corresponding to the following formula. l^0^. ^7^5×T=50~130 0.7<l<4.0 However, l is the processing length (unit: m) when the silver halide photographic light-sensitive material is processed, and T is the length of the photosensitive material. The material is above
This is the time (unit: seconds) required to pass through.