JPS58114035A - Method for processing silver halide black-and-white photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a rapid processing method superior in stability of a photographic image after processing and satisfying a short time processing condition, by adding at least one compd. selected from a group of specified compds. (A) and/or (B) to a processing soln. in an image stabilizing step of 3 steps consisting of a developing or alkali activating process, a fixing process, and this image stabilizing process. CONSTITUTION:The compd. group A is iodide of an alkali metal or ammonium, such as ammonium iodide, potassium iodide, or sodium iodide, and a desirable concn. in an image stabilizing soln. is 0.005-0.1mol/liter. The compd. group B is a heterocyclic compd. represented by general formulaI, embodied as formulae II-V, and a desirable concn. in said soln. is 5X10<-4>-5X10<-2>mol/liter. Preferable pH in the soln. is 4-9, and its temp. is 10-60 deg.C, and the stabilizing step of at 25 deg.C and 10sec processing gives superior result.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing silver halide black-and-white photographic materials, and more particularly to a method for processing silver halide black-and-white photographic materials that can be rapidly processed.

In recent years, processing steps for photographic light-sensitive materials have been becoming more and more rapid), and the case of silver halide black-and-white photographic materials is not out of the question. A stabilization processing method is currently employed as a fast processing method for black-and-white photographic materials. The stabilization treatment method is to remove the unexposed photosensitive silver halide t1 remaining in the photosensitive material by immersing it in a water solution containing thiocyanate after block image processing. This process converts silver into a stable silver complex that no longer shows any change when exposed to light. According to this method, since the water washing process can be omitted, the processing time can be significantly shortened.

However, this stable method has the following drawbacks.

The problem is that since thiocyanate has deliquescent properties, photographic materials subjected to stabilization treatment exhibit some stickiness.

Secondly, under certain severe conditions, thiocyanate may generate cyanide which is harmful to the human body, and its use is therefore undesirable from the standpoint of environmental pollution.

Third, photographic materials stabilized using thiocyanate are
-The point is that one's concentration tends to decrease or disappear. That is, the color of the image, which was initially black and white, changes to yellow or disappears during long-term storage. This phenomenon occurs particularly when the photosensitive 4IR family is stored under high humidity due to discoloration and fading.

And island 4 is that thiocyanate, as is well known, has a property 1i that easily decomposes metals.

Since the stabilization treatment method has drawbacks such as F1 or higher, there has been a strong desire for a new rapid treatment method to replace it.

As a rapid processing method for black and white photographic materials other than the known stabilization processing method, there is a processing method consisting of three steps: development processing, fixing processing and water washing processing.
It is often carried out in lagoons where the temperature is above ℃.

In order to further shorten the development time, it is possible to add a moderating agent to the photosensitive material in advance, and add an alkaline activating solution containing no or substantially no developing agent to the photosensitive material used in normal development processing. A rapid processing method is also known, in which a fixing process and a water washing process are carried out.

However, the above-mentioned rapid processing method consisting of the three steps of development (or alkaline activation), fixing, and water washing has a fundamental flaw.

That is, when the water washing process time becomes shorter, the Kyuden photosensitive composition that is immersed into the photosensitive material during the fixing process is not completely removed during the subsequent water washing process, but after the water washing process is completed. Since these materials remain in the photosensitive material, if the photosensitive material is stored for a long period of time after being processed, the image will fade.

Several methods are known for speeding up the removal of constant molar liquid compositions from photosensitive materials (by increasing the water washing efficiency). Examples include (1) using DeioII* ammonium as a fixing agent for sodium deosulfate, (2) pflt & combing the electrodeposition solution, (3) adding salts to the electrodeposition solution, ( 4) Increasing the IIt of the flushing water, (5) Increasing the flow rate of the flushing water, (6) Increasing the flushing efficiency by increasing the agitation or spraying the flushing water as in a one-way shower system. It has been known. However, no matter which method is adopted, there is a limit to reducing the washing time.
Particularly in the case of a short-time process in which the water washing process is completed within 30 seconds, it is extremely difficult to obtain stable images with little fading.

Furthermore, in recent years, it has become necessary to reduce the flow rate of washing water for reasons of preserving the burial mound, such as saving water resources and reducing the amount of treated waste liquid. However, if the rinsing water flow is too small, the electrodeposition liquid composition brought into the rinsing water will not be sufficiently diluted and will accumulate in the rinsing water. The toner remains in the photosensitive material, which deteriorates the durability of the image and causes discoloration of the image when stored for a long period of time.

Particularly, under low iron quantity washing conditions where the daily flow rate of washing water is less than the washing tank capacity, it is almost impossible to obtain stable ms with little fading.

As mentioned above, there is currently a strong desire for the emergence of a new rapid processing method to replace stabilization processing, but in order to obtain an alternative to stabilization processing, short processing times, which are the greatest advantage of stabilization processing, must be The entire processing step must be completed within 45 seconds at the latest. Furthermore, in order not to impair the simplicity, which is another advantage of the stabilization treatment method, it is necessary to keep the amount of treated attrium solution and waste liquid low.
Furthermore, the processing equipment must be made of four parts and inexpensive. It has not been possible to satisfy the above conditions using the conventional processing method consisting of three steps: development, electrodeposition, and water washing.

An object of the present invention is to provide a method that can be processed quickly and
An object of the present invention is to provide a method for processing a silver halide black-and-white photographic light-sensitive material, which provides excellent stability of subsequent photographic images.

Another object of the present invention is to provide a method for processing silver halide black-and-white photographic materials, which can significantly reduce the amount of light and the amount of Ii solution used in image stabilization processing.

Honroku #i@ is an extremely superior processing method for black-and-white photographic materials that consists of three steps: dust treatment and image stabilization as a processing method to achieve the above purpose. I found out.

Furthermore, the present invention is a black-and-white photographic process consisting of the above three steps.
In the method of processing K material, 1 mg 1 stabilization treatment jM
A treatment method comprising at least 1 site of a compound selected from the following compound compound #(4) and/or the following compounds in I solution (hereinafter referred to as IIM stabilizing solution), iWL was identified as a particularly excellent method for achieving the above objectives.

Compound group (A): alkali metal or ammonium iodides.

Compound m(at; a compound represented by the following general formula [11].

General formula [1] (In the formula, 2 represents a nonmetal atom spt necessary to create a 5- to 6-membered heterocyclic nucleus containing multiple X groups, and X is a water 1/A atom, an alkali metal atom, or an ammonium or organic amine residue (represented) Specific examples of iodides represented by compound group (4) include ammonium iodide, potassium iodide, and sodium iodide. The concentration of iodide contained in the 1ilil image stabilizing solution is preferably 0.001 mol/l to 0.2 mol/l, and if the appetizer contains o, o o s mol/l - 0.1 mol/l. desirable. If it is less than 0.001 mol/l, there is no effect on image stabilization (if it exceeds 0.2 mol/l',
On the contrary, the color fading of the image increases.

Heterocyclic % formula in compounds represented by compound group (B) % l of triazine, tetrazainde 7? ! Preferably, it is selected from r nuclei.

Specific examples of the compounds represented by compound group (S) include the following compounds.

Below, I: [Feeding Compounds] [213[22] These compounds represented by Compound #(B) that can be used in the present invention can be used in the U.S. Lii% Permit No. 3,615°501, No. 2,324 .12: No. 1, 2,384
．． No. 593, No. 2,496.940, No. 3,137.
578, 2,496.940, 413.082.
No. 088, 1ili13゜473.924, 3,5
No. 75.699, fli No. 13.687.660, fli No. 2
, No. 271.229, No. 2.49 Li2O, British Patent No. 111,141.773, No. 1.37@, No. 600, #4a, etc., or synthesized into a container according to the method described therein. can do. Also, edited by Fujio Kotake, Great Organic Chemistry (Asakura Shoten, 1971'#i) or Nie Weigsbager, The Chemistry of Heterocyclic Combus/Weigsb@r
g@r, Th@Chemistry ofh@taro
cyc1ic compounds N, Y, Int@
rsci@ncs, 1950-1964), or according to the method described therein.

It is desirable that the image stabilizing air eta of the compounds represented by compound group (B) be at least 5X10 to 5X10 mol/l, particularly preferably 5X10 to 5X10 mol/l. No effect on image stabilization.

In the present invention, one or more types of compounds selected from compound #(A) are used, two or more types of compounds selected from the compound group #i are used, and compound group members and compound 11i are used. It is also convenient to use a combination of at least lli selected from each of (II).

The electrolyzed solution used in the present invention can contain various kinds of (D). Various antifungal additives can be added for the purpose of preventing the generation of microorganisms in the feed. .Specific insecticides include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-phenyl 7x 7-l, yo loaene, dichloro 7-ene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester.

2-(4-thiazolyl)-benzimidazole.

Benzisothiazolin-3-one, Dodeflubenzirudimethyla/monium chloride, N-(Fluorodichloromethylthio)-7talimide, 2.4.4'-
)lichloro-2'-no)hydrooxydiphenyl ether and the like.

Various chelate agents can be added to the image stabilizing liquid used in the present invention for the purpose of sequestering metal ions. Specific examples of chelate heirs include ethylenethiaminetetraacetic acid and nitrilo! Acetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminewood vinegar 51.1.3-diamino-2-prono; aminopolycarboxylic acids such as ethanolic acetic acid, nitrilo-N,N,N-trimethylenephospho/acid, ethylenediamine-N, Aminopolyphosphonic acids such as N,N'-tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1-dolphoxyethylidene-1,1-diphosphonic acid, 1-amino-ethylidene-1,1-diphosphonic acid, etc. Neutralization of alkylidene diphosphonic acid, 2-phosphono-butane-1,2,4-)licarbo/
Examples include acidic phosphonocarboxylic acid, sodium hexametaphosphate polyphosphate, citric acid, and gluconium oxocarboxylic acid.

A surfactant of various types can be added to the image stabilizing liquid of the present invention for the purpose of preventing unevenness of water droplets. As the surfactant, any of cationic type, anionic type, nonionic wrinkles, and inner ionic dust may be used. Specific examples of surfactants include compounds described in ``Surfactant Wholesale 1 No. 1'' published by Kogaku Tosho ■.

The image stabilizing solution of the present invention contains sodium sulfite, potassium sulfite, ammonium, sodium metabisulfite, aqueous sodium sulfite, ii. acid sodium,
Various salts such as sodium vertate and sodium metaborate can be added.

The pH of the image stabilizing solution of the present invention is usually about 3-11, preferably about 4-9.

The amount of light emitted by the image stabilizing liquid of the present invention can be freely set depending on the conditions of use. As far as the purpose of image tube electrification is concerned, lI! Similar to the water washing treatment of I-Tomi, the higher the amount of fertilization, the more favorable the result. However, in order to achieve a significant reduction in the amount of processing waste liquid, which is another objective of the present invention, the amount of light per day of the image stabilizing solution should be less than the capacity of the Im image stabilizing processing tank. There is a need to. By using the rapid processing method 1m of the present invention, which consists of three steps of development processing, electrodeposition processing, and image stabilization processing, it is possible to obtain an image with excellent stability even under such low surface conditions. can. Under such low light conditions, it has been impossible to obtain stable images using the conventional rapid processing method consisting of three steps of development, fixing and washing.

As the processing solution (hereinafter referred to as 31* solution) used in the development process of the present invention, one having a commonly used composition can be used. 'fj44a main drug is Hyde C
quinones, alkylhydroquinones (e.g. methylhydroquinone, dimetylhydroquinone, t-butylhydroquinone), catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, methoxyhydroquinone, ethoxyhydroquinone/, aminophenol Jn King II (Tatoe tfN-methyl-p-aminophenol, 2゜4-diaminophenol), ascorbic acid developer + drug, N-methyl-p-aminophenol ruaate, pyrazolone II (e.g. 4-aminopyrazolone), 3-pyrazolidone developing agent ( Parable ---
--------1-7x Nil-3-Bira/17 Don, 1-
,yenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, l-7enyl-4-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, t-p-hydroxy Phenyl-4,4-methyl-3-pyrazolidone) groups are used singly or in combination. %, a combination of hydroquinone and 3-pyrazolidones or a combination of hydroquinone and aminophenols is suitable for this rapid treatment.

The dust image solution of the present invention may also contain -sulfate, j
Preservatives such as M curved acid salts, human mixylamines; alkaline compounds such as hydroxides, IA salts, and phosphoric salts; pH-preservatives such as acetic acid; Minatokaisuketsugu such as polyethylene glycol m: Sensitizers such as ammonium salts: organic compounds such as methanol, diethylene glycol, jetanolamine, dimedelformamide, dimethylsulfoxide, etc.
Tsugu; Development promoting Dotsugu; Kai-active line; Antifoaming Tsugu; Color 1111 Tsugu;
Adding viscosity such as carboxymethylcellulose and hydroquinetherylulose, hard a# such as geltaraldehyde: silver sludge prevention; thioether, thioamide 1
Silver 1I such as deocyanate, thiosulfate, etc.
IJ! Il: potassium bromide, benzotriazole, 2-
Antifogging agents such as mercaptobenzothiazole and 1-7enyl-5-mercaptotetrazole; Various additive steels such as medium-rate steel such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid [can be contained] .

Further, if a developing agent has been added to the light-sensitive material in advance, there is no problem in replacing Klfi and the development@jl of the present invention with an alkali activation treatment.

Treatment 1I used for alkali activation treatment in the present invention
II#L (hereinafter referred to as Alkaline Activated Shuku) Co., Ltd., and any other ingredients other than the visual drug used in the usual Shiratori fJ4m liquid can be included. The pH of the wrinkle alkali activating solution is usually about 10-14, preferably about 11-14.

As the processing liquid (hereinafter referred to as electrodeposition liquid) used in the fixing process of the present invention, those having compositions commonly used can be used. i! Sodium thiol, ammonium thiosulfate, sodium thiocyanate as a vehicle,
In addition to silver halide metals such as thione ammonium, thio amine conductor, sodium chloride,
Ammonium sulfate, sodium bisitate, sodium metasulfate
IN such as potassium sulfate! Sulfate; S acid, m-, meta-
arIIt salts such as IJum; organic carboxylic acids such as acetic acid, citric acid, tartaric acid, apple mold, ii*,
Inorganic acids such as hydrochloric acid; Amine #A such as ethylenediamine, jetanolamine, triethanolamine; Water bathable aluminum salts such as potash light bread, ammonium light bread, -acid aluminum, aluminum chloride; methanol,
It can contain organic compounds such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol, and acetone, and if necessary, iodides such as potassium iodide and sodium iodide, and other additives. .

3 dust image disposal, fixing processing and image stabilization processing of the present invention
When carrying out a processing method consisting of steps, each step is usually carried out at about 10 DEG C. to 60 DEG C., but only the development process is preferably carried out at about 20 DEG C. to 60 DEG C.

The silver halide black-and-white photographic light-sensitive material processed by the processing method according to the present invention may be used for any purpose, and the silver halide in the commonly used silver halide photosensitive emulsion layer on the support is , silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and the like. Further, the silver halide black-and-white photographic light-sensitive material processed according to the present invention is negative! ! It may be either a fixed temperature or a positive temperature.

The processing of the present invention is not limited to automatic processing using an automatic processing machine or the like, but any known 1a! II developing hand plate 1 can be used.

Hereinafter, the present invention will be explained in more detail with reference to the following examples, but the practical implementation of the present invention is not limited thereto.

Example 1 A lump image solution, an electrodeposition coating solution, and a J image stabilizing solution were prepared having the following compositions.

椀儂水螋淑(f tQQ10y%=T:)A 200jrm
Image Stabilizing Liquid A sample (silver amount 2.5 g/wl) of a black and white photographic light-sensitive material having a silver iodobromide (iodide*O, S mole) gelatin emulsion layer on a polyethylene terephthalate support was imagewise exposed. Thereafter, it was processed in a roller conveyance type automatic developing machine containing the above developer, fixer and il image stabilizer. The tank capacity of the automatic developing machine is 2 tons for development processing, fixing processing, and image stabilization processing. Processing I! & was developed at j1B at 8° C., fixing section at 1135° C., and image stabilization at 25° C., and the processing time was 15 seconds for development, 15 seconds for fixing, and 10 seconds for IIM stabilization. The amount of light was 30 Od for the developer, 300 mg for the fixer, and 20 G for the photosensitive material P#1.

As for Hikankai, the developing treatment and the fixing treatment were the same as those described above, and instead of the image stabilization treatment, a treatment method was adopted in which normal washing with water was also performed. In this case, the light intensity of the washing water is 21 for general processing photosensitive material IM/4, and the washing water mf is 2.
The water washing time was 10 seconds at 5°C.

#Jiewei The lightless sample was processed for 7 consecutive days at 5°C per day, and finally the sample was passed through a step wedge and exposed to sunlight. Sample t-obtained. The #C material was exposed to a defined wedge at 1 [* and then the #C material was heated to a high temperature (70°C).

8011RH) for one week, and then the permeable layer of each stage was added again. I of each stage due to preservation under Tamegata high humidity
The smaller the decrease in l[, the better the image stability. The Mth power is shown in Table-1. Here, the loss of processing g* is 1
indicates the drop in placement of the stage closest to 1.0.2.0.3.0.

As is clear from Table 1, the ovmm stability of the sample processed by the method of the present invention is such that the II light intensity of the image stabilizing solution is less than enough of the washing water ring light intensity in the water washing method adopted as a comparison method. It can be seen that this method is extremely superior to the water washing method because it requires very little effort.

Example 2: Alkaline activating solution, fixing solution and ms having the following compositions:
A stabilizing solution was created.

Alkaline Activating Solution Fixer-1 Stabilizing Solution Silver chlorobromide (bromide fl1
A sample of black and white photographic paper (silver content 1.2 g/, wl) was exposed imagewise with a general gelatin milk layer and a wrinkled milk layer containing a silver mole of hyde in the wrinkled milk layer. Thereafter, the film was processed in a roller conveyance layer automatic developing machine containing a primary alkali activating solution, a fixing solution, and an image stabilizing solution. The tank capacity of the automatic dusting machine is for alkali activation processing, fixing processing,
- Both of my stabilization treatments are 21. Processing 1! Ij was 25° C. in all three treatment steps, and the treatment time was 610 seconds in all three treatment steps. Alkaline activation treatment #i
Kako method [How to update all liquids every week without removing]
The fixing process and Ii image stabilization process are performed using the supplementary light method [t! & used. The amount of light was 200-200 for both the fixing solution and the ijg1 stabilization sample per 1 dK.

Ratio 1 [as alkali activation treatment and fixing treatment JII
fi was the same as the above-mentioned method, and instead of the Ij11 stabilization treatment O, a treatment method was adopted in which a normal water washing layer was applied. Here, the light amount of the washing water is 2t per 1+/, and the washing water i
The temperature was 2t1°C, and the water washing time was 10 seconds.

A sample of black-and-white photographic paper that had been previously exposed to light was treated with Sd per day t-1 for 7 consecutive days, and finally the sample was exposed to sunlight using a step wedge seven times.
A sample for image stability evaluation was obtained.

Reflection 1 of each stage of the sample exposed to −1 wedge after processing
1 [tllll determined, followed by this test at high-Afi
(70C, 80 long wing H) After storing it for one hour, the reflective chain & of each stage was adjusted again. The smaller the decrease in density of each stage due to storage at high temperature and high humidity, the better the image stability. 5ift-shown in Table-2. Here, @j
The concentration of l[il is 1.0.

1.5.2.0 shows the decrease in at of the stage closest to 1.5.2.0.

As is clear from Table 2, the stability of the sample treated by the method of the present invention is such that the light intensity of the 'raB stabilizing solution is sufficient for the water damage light intensity in the water washing method adopted as a relative softener. It can be seen that this method is extremely superior to the water washing method, although it is less than 4.

The following margin procedural amendment (voluntary) April 2j, 1980 Haruki Shimada, Commissioner of the Patent Office Tono 1 Indication of the case 1988 Patent Application No. 20981 Snoring 2 Invention t7) Name 15 ...Silver Genide Black and White Photography Naruko Material processing method 3
Relationship between the person making the amendment and the case Patent applicant 5''';1 4, agent 〒105 6 Number of inventions increased by amendment As shown in the attached sheet.

The statement of contents of the amendment shall be amended as follows - 6(1) No. 1
Add the following text between lines 15 and 16 on page 6.

Various organic solvents can be added to the image stabilizing solution of the present invention. Specific examples of organic solvents include compounds described in "Solvent Handbook" published by Kodansha.

that's all

Claims (1)

[Claims] Consisting of three steps: bulk treatment or alkali activation treatment, fixing treatment, and image stabilization treatment, the following compound group (A) and/or 1. A method for processing a silver halogenide black-and-white photographic light-sensitive material, which comprises at least 1111 compounds selected from the following compound groups. Compound group: alkali gold 17s or ammonium iodide. Compound #(B): Compound represented by the following general formula [visually]. General formula [11 (wherein 2 represents a group of nonmetallic atoms necessary to form a heterocyclic nucleus t containing a 5- to 6-membered aS term, and X represents a water atom, an alkali gold atom, ammonium or Fi (Represents an organic amine residue.)