JPH02157748A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To recover development activity so that good development can be continued by adding an alkaline agent to a developing soln., which is fatigued by developing, thereby increasing the pH of the developing soln. CONSTITUTION:For example, the alkaline agent is added to the developing soln. to increase the pH thereof to about 0.2 to 0.6 on increasing of the quantity of halogen ions to about half the final value which is an equiv. running concn. The alkaline agent is again added to the developing soln. to increase the pH thereof by about 0.2 to 0.6 when the quantity of the halogen ions in the developing soln. increases to attain about 3/4 the final value. The pH of the developing soln. is thus adjusted until finally 12 to 13 is attained. The developing soln. which is recovered from the fatigue, more particularly from the fatigue by processing by adding the alkaline agent thereto is used at the time of developing the exposed photosensitive material. The efficient use of the developing soln. is possible in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for developing silver halide photosensitive materials such as black-and-white films, black-and-white papers, color films, and color papers, in particular, to efficiently use a developer. The present invention relates to a development processing method.

[Conventional technology]

When performing black-and-white development or color development of silver halide photosensitive materials in a developing tank containing a developer, fresh developer is replenished according to the amount of silver halide photosensitive material processed in order to ensure uniform development characteristics. , the exhausted developer is discharged from the developer tank by overflow or the like. This is because as the amount of development processing of the silver halide photosensitive material increases, the concentration of halogen ions in the developer increases due to elution from the silver halide photosensitive material. This is because it reduces activity. Therefore, even though a considerable amount of the developing agent remains in the developer, the developer is currently discarded because the developing activity is reduced.

In particular, since color developing agents are expensive, it is not economical to discard a developer solution in which a significant amount of the developing agent remains. It is desired to develop a development processing method that can obtain the desired results.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a development processing method that allows efficient use of a developer.

[Means to solve the problem]

In the present invention, when developing a silver halide photosensitive material, when an alkaline agent is added to the developer exhausted by processing to increase the pH of the developer, the pH of the developer is increased to a certain level, especially above the initial pH or running equilibrium pH value. This was done based on the knowledge that if the temperature is increased within this range, the development activity of the developer is recovered and good development can be continued, and the above problems can be efficiently solved.

That is, the present invention is characterized in that when developing an exposed silver halide photosensitive material, a developer is used in which an alkaline agent is added to recover the fatigue of the developer, particularly the fatigue caused by processing. A method for processing photosensitive materials is provided.

Examples of the developer used in the present invention include a black and white developer and a color developer (including a developer used for color reversal).

In the present invention, as the alkali agent for increasing the pH of the developer, alkali metal hydroxides such as sodium hydroxide and calcium hydroxide, ammonia, etc. are used as they are, or those with a high concentration, such as alkali metal hydroxide 40
It is preferable to use a solution obtained by dissolving 11 g or more of water in 11 g of water. In the present invention, it is possible to use the developer easily and effectively by using an alkaline agent, but if an unstable agent such as a developing agent is used together with the alkaline agent, the above-mentioned convenience may be compromised. I don't like this because it can cause damage. However, necessary additives may be included as long as they do not impair convenience.

When a photosensitive material is developed, halogen ions are eluted from the photosensitive material, and as the amount of processed photosensitive material increases, the amount of halogen ions in the developer increases until it reaches a constant value (final value).
, that is, approaches the running equilibrium concentration, but in the present invention,
When the amount of halogen ions increases to about half of the final value, the above alkaline agent is added to adjust the pH of the developer to 0.2-0.
When the amount of halogen ions in the developer increases to about 3/4 of the final value, add an alkaline agent again to raise the pH of the developer by about 0.2 to 0.6. and finally adjust the pH of the developer to 12-13. In other words, this operation eliminates the fatigue of the developer and makes effective use of the developer. Although the example in which the alkaline agent is added twice has been described, the number of additions can be further increased.

In the present invention, when performing the above-mentioned development, the amount of developer that is discarded is reduced by replenishing the developer tank with an amount of developer that is approximately equal to the amount of developer that adheres to the photosensitive material and is taken out of the developer tank. A great advantage is that it can be completely eliminated. In other words, in the past, when the amount of developer replenisher was 100, 20 of this amount adhered to the photosensitive material and was taken out of the developer tank, and the remaining 80 was discarded as overflow from the developer tank. It is possible to eliminate such overflows.

The developing method of the present invention can be carried out using a conventional tank-type development processing tank, such as a method using a single tank type or a multi-stage tank (for example, 2 to 4 tanks).

When the development is carried out in one tank, the developing agent can be effectively utilized for a long period of time by adding an alkaline agent-containing aqueous solution containing no developing agent to the tank. At this time, while monitoring the pH in the tank, [If the pH rises or falls above a certain pH, the pH rises by 0.1 to 0.9, preferably by 0.2 to 0.6, from the initial pH of the developer. It is preferable to add an alkaline agent so as to

Further, when there are multiple developing tanks (tanks), it can be carried out as follows.

For example, in the case of three tanks, (a) Replenish the first tank for development processing with developer replenisher according to the amount of photosensitive material to be processed, add an alkaline agent to the overflow solution, and use that solution for development processing. A method of continuously processing a photosensitive material while adding an alkaline agent to the overflow liquid of the second developing tank in addition to the second tank, and adding the solution to the third developing tank. The amount of alkaline agent to be added here is 0.0.
It is preferable to use an amount that increases the amount by 1 to 0.9, preferably 0.2 to 0.6. Further, the alkaline agent may be directly added to the second tank (intermediate tank) and the third tank.

(b) A method in which the above method (a) is continuously processed using a slit-type automatic processor.

(c) A method in which the amount of replenisher used during development processing is reduced to 18 to 38, which is the conventional level, using the methods (a) and (0) above.

In the above methods (a) to (c), a method may be used in which the pH of the overflow liquid or tank liquid is measured and an aqueous solution containing an alkaline agent is added when there is a deviation of more than a certain value. A method may be used in which an aqueous solution containing an alkali agent is added in an amount determined depending on the photosensitive material depending on the processing amount of the photosensitive material. The same procedure can be carried out in the case of 2 tanks or 4 or more tanks.

In the present invention, plate development can also be performed. In this case as well, the pH of the developer can be monitored as in the case of using one tank, but based on experience, an alkaline agent is added depending on the number of sheets to be processed, and the pH of the developer is adjusted to 0.2 to 0. 6
It is better to raise it.

In addition to the above-mentioned method, the development processing method of the present invention is preferably a method in which a slit-shaped processing path is filled with a developer and a photosensitive material is passed through the processing path for development, that is, so-called slit development.

Here, a slit-shaped processing path is defined as a cross-section that is equal to the width (in the width direction of the photosensitive material) when the passage in the processing tank through which the photosensitive material passes is cut at right angles to the traveling direction of the photosensitive material. This means that it has a thin so-called slit shape. Note that the cross section of the slit shape may be rectangular or oval.

The shape of a processing tank having such a slit processing path is defined as follows.

V/L≦20, particularly preferably V/L≦10. Here, ■ is the volume (cat) of the processing liquid accommodated in the processing path, and L is the center path of the photosensitive material from the liquid level on the inlet side of the processing tank to the liquid level on the exit side (processing path ) is the length (cm).

Therefore, the slit processing path is characterized by a small amount of liquid accommodated relative to the length of the path. In other words, since the amount of liquid is small, the liquid in the processing path (processing tank) can be replaced quickly by replenishing the processing liquid. In other words, the residence time of the liquid in the processing tank is shortened, and fatigue of the processing liquid over time can be avoided. Can be done. However, for practical purposes, the lower limit of V/L is preferably 0.1, particularly preferably 0.5.

In the processing path, specifically ■ is toooo ~ 100c
n! is preferable, particularly preferably 5000 to 200 cI
11. Most preferably 1000-300c++! It is. Further, L is preferably 300 to 10 cm, particularly preferably 200 to 20 cm, and most preferably 100 to 30 cm.

When processing is performed using a slit processing path, the liquid volume V (cd
) It is preferable to use a processing tank in which the liquid area S (CrI) (hereinafter referred to as opening area) in contact with air is small.

Specifically, it is preferable that V and S have the following relationship.

S/V≦0.05, particularly preferably S/V≦0.01. In other words, S/
The smaller V is, the less air oxidation occurs, and the less evaporation of the liquid, the more the liquid can be stored stably for a long period of time.

However, practically, the lower limit is preferably 0.0005, and particularly preferably O, OO1.

In the above regulations, the thickness of the slit-shaped processing path is 1 to 50
Dwarf fish are preferred, and 3 to 30 aun are particularly preferred.

In addition, the conveyance speed of the photosensitive material in the slit processing path is 10 cm.
/min to 300cm/min is preferable, and in particular, to obtain an even and uniform finishing performance, the range is 20 to 2O-()co+
/min range is preferred, most preferably 20-120c
m/min.

When processing is performed in the above slit processing path, changes in the processing solution in the processing tank occur, specifically, oxidation of the developing agent and preservative, decrease in pH due to absorption of carbon dioxide in the air, and concentration due to evaporation of water. , various decompositions of treated liquid components due to long-term residence in the tank,
This has the great advantage of eliminating factors of variation in conventional processing, such as mutual unfavorable reactions. Therefore, even in slow processing where the amount of photosensitive material to be processed is small, it is possible to perform processing in which the finishing performance of the photosensitive material, such as gradation, fog, and sensitivity, is less likely to fluctuate. Furthermore, it is easy to make the processing apparatus more compact, and since the opening area is small, the complexity of using a conventional floating lid can be avoided.

In the present invention, the slit-shaped processing path includes one in which at least a portion of the portion other than the roller for conveying the photosensitive material is slit-shaped, and the length of the slit-shaped processing path between the conveyance roller and the roller is The length should be 5 cai or more, preferably 10 cm or more.

Note that a flexible member (such as nylon or polyester) can be provided on the inner wall of the slit-shaped processing path so as to protrude inward.

In the present invention, when performing slit development, it is further preferable to use a processing tank in which the ratio of the liquid surface area to the liquid volume is small, and in this processing tank, the cross-sectional area of the processing liquid path is approximately the same as the surface area of the liquid surface part. This is preferred, and so-called thin layer development is preferred.

Furthermore, the liquid flow path in the main part of the developing tank and the conveyance path of the photosensitive material are almost parallel, and in the main part, the liquid flow path in the main part of the developing tank is perpendicular to the emulsion layer and the support layer of the photosensitive material (thickness direction).
The length is within 200 times the thickness of the photosensitive material, and more preferably 2 to 20 times the thickness of the photosensitive material.
Preferably, the processing liquid path is 100 times larger, particularly 5 to 50 times larger. In this case, the gap between the processing tank and the photosensitive material in the thickness direction is 0.3 to 30 mm, preferably 0.5 to 10 m.
l111 is particularly preferably 0.5 to 3 am.

In the present invention, in addition to filling the developing solution into the slit-shaped processing path, bleach solution, bleach-fix solution, fixing solution, washing water, stabilizing liquid, etc. used in the processing step after development are also filled into the slit-shaped processing path. , an exposed silver halide photosensitive material can be passed through them for development processing.

Specifically, the slit developing method of the present invention includes the following steps.

(1) Development - Bleach fixing - Washing - Drying (2) Development - Bleach fixing - Stabilization - Drying (3) Development - Bleach fixing - Washing - Drying (4) Development - Bleach fixing - Stabilization - Drying (5) )Development - Bleach, Fixed, Wash, Stabilize, Dry (6) Development - Bleach, Fix, Wash, Stabilize, Dry (7) Black and white development - Wash, Reverse, Color development - Wash, Bleach, Wash, Stabilize, Stabilize. Water washing can be provided between development and bleaching in the above processing steps. Furthermore, steps such as stopping, adjusting, and neutralizing can be provided as appropriate.

Incidentally, in the case of a black-and-white photographic material, the bleaching step and the stabilizing step can be omitted in the above (3) to (5).

In the above-mentioned slit developing method, in the present invention, the slit-shaped processing path is divided into three parts, such as first to third processing tanks, as shown in FIG. After filling the developer with the developer, the first processing tank into which the photosensitive material is first introduced during the processing of the photosensitive material is replenished with fresh developer, and then the alkaline agent is added to the second processing tank. Increase the pH of the developer by 0.2 to 0.6, and further add an alkaline agent to the third processing tank to increase the pH of the developer by 0.2 to 0.6.
It is preferable to carry out development by raising the temperature. On this occasion,
It is preferable to adjust the pH of the final developer to about 11-13.

Separately from the above method, slit development is performed for 3 minutes, the first minute is developed with fresh developer, an alkaline agent is added in the first minute to increase the pH of the developer, and after another minute, Development can be carried out by adding an alkaline agent to further raise the pH of the developer. In any of the above methods, if the amount of developer refilled to the first processing tank is equal to the amount taken out by the photosensitive material, the amount of developer discharged can be completely eliminated, and development can be performed in a non-discharge method. be able to.

On the other hand, the bleaching solution, bleach-fixing solution, fixing solution, washing water, stabilizer, etc. used in the post-development process are different from the order in which the developer is supplied, and are supplied in a direction countercurrent to the direction in which the photosensitive material is transported. That is, 30 to 70%, preferably 40 to 60%, of the replenishment amount of the processing solution is supplied from a supply port provided at a position where the photosensitive material exits from the processing solution, and the remainder is divided according to the number of supply ports. It is preferable to supply the photosensitive material from a supply port provided upstream of the position where the photosensitive material comes out.

Note that the amount of replenishment of each processing solution is arbitrary, but in the case of a photosensitive material with a width of 82.5 mm, it is 3 to 30 ml per 1 m of photosensitive material,
Preferably, it is 5 to 20 d, and when processing is performed with this replenishment amount, low replenishment and excellent finishing performance can be obtained.

Although the slit-shaped developing system is basically configured as described above, the apparatus used in the present invention can be equipped with a temperature regulator, a roller, a replenishment port, an overflow port, etc., which are included in a normal automatic developing machine. Further, the photosensitive material can be moved within the processing path by any conveyance method such as roller conveyance, leader belt conveyance, cine strip type, or rotating drum type.

Next, the processing liquid used in the processing method of the present invention will be explained.

Development Treatment In the present invention, a color developer or a black and white developer is used as the developer.

Among these, the color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phinidine diamine compounds are preferably used, and a representative example thereof is 3-methyl-4-amino-N.

N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Mention may be made of ethyl-N-β-methoxyethylaniline and its sulfates, hydrochlorides or p-)luenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose. The above color developing agent is 0.1 to 5% by weight in the developer,
Preferably it is contained in an amount of 0.3 to 1.0%.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2゜2.2]octane) various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Various acidifying agents such as acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, and 1-hydroxyethylidene. -1
, 1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'N'
-tetramethylenephosphonic acid, ethylene glycol (0
-hydroxyphenylacetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as diμ-droxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. can be used alone or in combination.

The pH of the mother liquor of these color developing solutions and black and white developing solutions is generally 8 to 12, preferably 9 to 10.5.

Bleaching and/or fixing treatment (desilvering treatment) After color development, a bleaching treatment is usually performed. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment. Furthermore, processing in two consecutive bleach-fixing baths, or carrying out a fixing process after a bleach-fixing process can be carried out as desired depending on the purpose. As a bleaching agent, for example, iron (■), Kobal) (III
), chromium (■), compounds of polyvalent metals such as copper (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (DI) or cobalt (II);
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; Sulfate: bromate; permanganate; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(I[I) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(II[) complex salts is usually 5.5 to 8, but in order to speed up the processing, processing may be performed at an even lower pH. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Useful bleach accelerators include those specifically described in U.S. Pat.
No. 893.858, West German Patent No. 1.290.812,
Compounds having a mercapto group or disulfide bond as described in JP-A No. 53-95630, Research Disclosure No. 17,129 (July 1978), etc.;
Thiazolidine derivatives as described in JP-A-50-140129; thiourea derivatives as described in US Pat. No. 3,706,561; iodide salts as described in JP-A-58-16235;
Examples thereof include polyoxyethylene compounds described in West German Patent No. 2.748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect, and are particularly preferred as described in US Pat. No. 3,893.
．． Preferred are the compounds described in No. 858, West German Patent No. 1.290.812, and JP-A-53-95630. Furthermore,
Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

Water Washing and/or Stabilization Process After the above desilvering process, a water washing and/or stabilization process is generally performed. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociet.
y of Motion Pi〔ture and Te
1evision Engineers Volume 64,
P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorinated disinfectants such as chlorinated sodium incyanurate,
Others (benzo) 177 sol, etc., “Chemistry of antibacterial and antifungal agents” by Hiroshi Horiguchi, “Sterilization of microorganisms, sterilization, and antifungal technology” by Hiroshi Horiguchi, “Encyclopedia of antibacterial and antifungal agents” edited by the Japan Antibacterial and Antifungal Society ” can also be used.

The pH of the washing water used is 4-9, preferably 5.
-8. Washing water temperature and washing time also depend on the characteristics of the photosensitive material.
Although various settings can be made depending on the purpose, generally the temperature is 15-45°C for 20 seconds-10 minutes, preferably 25-40°C for 30 seconds-5
A range of minutes is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. Such stabilization treatment is described in Japanese Patent Application Laid-Open No. 57-8
No. 543, No. 58-14834, No. 60-22034
The known method described in No. 5 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

Over 70- due to water washing and/or replenishment of stabilizing solution
The liquid can also be reused in other processes such as the desilvering process.

Photosensitive materials processed by the method of the present invention include color photosensitive materials as well as black and white photosensitive materials. For example, color paper
In addition to color reversal paper, color negative film for photography, color reversal film, negative or positive film for cinema, and direct positive color photosensitive materials, examples include X-ray film, photosensitive materials for printing, microfilm, and black and white film for photography. can.

Any known silver halide emulsion for light-sensitive materials can be used. Silver chlorobromide emulsion (silver chloride content of 90 mol % or more is preferred for rapid processing) is used for color printing photosensitive materials, and silver iodobromide emulsion (containing silver iodide) is used for color photosensitive materials for photography. The amount is preferably 2 to 15 mol%). In particular, in slit development, it is preferable to use a silver chloride photosensitive material because no bromide ions are released into the developer, and development unevenness due to non-uniform dispersion of bromide ions is less likely to occur. Moreover, since the developing speed is fast, the length of the slit processing path can be shortened, the processing apparatus can be easily made compact, and non-uniform distribution of the concentration of the processing liquid can be eliminated, which is preferable. Silver halide grains are spherical, cubic, octahedral, rhombic dodecahedral, tetradecahedral, etc., and tabular (preferably aspect ratio 5 to 20) are used for high-sensitivity photosensitive materials.
is preferred. These particles may have a uniform phase or may have a multilayer structure. moreover,
The particles may be surface latent image type particles or internal latent image type particles. The particle size distribution may be polydisperse or monodisperse (preferably standard side difference/average particle size≦15%), but the latter is preferred. These silver halide grains may be used alone or in combination depending on the purpose.

-The above photographic emulsion is subject to Research Disclosure (RD)
) vol, 176 ItemNcf7643 (L■
, ■) (December 1978).

Furthermore, emulsions that have been subjected to physical ripening, chemical ripening, and spectral sensitization can usually be used. Additives used in such processes are listed in Research Disclosure Vol. 176, Nα17643 (December 1978) and Research Disclosure Vol.
It is described in Volume 87, Nα18716 (November 1979), and the relevant parts are summarized in the table below.

Furthermore, known photographic additives that can be used are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

Additive type 1 Chemical sensitizer 2 Sensitivity enhancer 4 Super sensitizer 5 Brightener 7 Coupler 8 Organic solvent UV absorption side stain inhibitor dye image stabilizer Hardener binder Plasticizer, lubricant 17 Static inhibitor RD 17643 RD 1871623 pages
Page 648 Right column Same as above Same as above Same as above 24 Page 25 Page 25 Same as above 25 Page Right column 25 Page 26 Page 26 Page 27 Page 27 Same as above Same as above Same as above Same as above 650 Pages left to right column Same as above 651 Page Left column Same as above 650 Page Right column Same as above Color light-sensitive materials can contain various color couplers, specific examples of which are disclosed in the above-mentioned Research Disclosure (RD) Nα17643, 1-C-G patent.

As dye-forming couplers, couplers that provide the three subtractive primary colors (i.e., yellow, magenta, and cyan) in color development are important, and diffusion-resistant, 4-equivalent or 2-equivalent couplers are important.
As specific examples of equivalent couplers, in addition to the couplers described in the above-mentioned patents described in RD17643, ■-○ and section D, the following can be preferably used.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide a deep color density.

Examples of magenta couplers that can be used include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used include hydrophobic, diffusion-resistant naphthol and phenolic couplers.
Preferably, a two-equivalent naphthol coupler of oxygen atom separation type is mentioned as a representative example. Also, couplers capable of forming cyan dyes that are stable against humidity and temperature are preferably used; typical examples thereof include U.S. Pat.
2.002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, a 2.5-diacylamino-substituted phenolic coupler, a phenylureido group at the 2-position, and a 5 These include phenolic couplers having an acylamino group at the -position, 5-amidonaphthol cyan couplers described in European Patent No. 161626A, and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Specific examples of magenta couplers are described in US Pat. No. 4,366,237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
It is written in No. 0, etc. Specific examples of polymerized magenta couplers are described in U.S. Pat. No. 4,367,282 and elsewhere.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler that releases the development inhibitor is the aforementioned RD1?643, ■
The patent couplers listed in Sections .-F. are useful.

In the light-sensitive material processed in the present invention, a coupler that releases a nucleating agent or a development accelerator or a precursor thereof in an imagewise manner during development can be used. Specific examples of such compounds are given in British Patent No. 2,097.140;
．． No. 131.188.

In addition, DIR described in JP-A-60-185950 etc.
Redox compound releasing coupler, European Patent No. 17330
Couplers that release dyes that exhibit yellow color after separation, as described in No. 2A, can be used.

〔Effect of the invention〕

Conventionally, a developing solution in which a considerable amount of developing agent remains is discarded, but according to the present invention, it is possible to provide a developing processing method that allows the remaining developing agent to be used effectively to the end. Furthermore, if the amount of developer replenishment is made equal to the amount taken out by the photosensitive material, the amount of developer waste can be substantially reduced to zero.

Further, according to the method of the present invention, a certain level of processing stability can be easily obtained without using a replenisher having a complicated composition containing a developing agent or the like.

Next, the present invention will be explained with reference to examples.

〔Example〕

Example 1 Fuji Photo Film black and white photographic paper Fuji Pro WP Paper 3
Dish development and non-replenishment processing were performed using a black and white developer with the following composition; fixer Fujifix (manufactured by Fuji Photo Film).

Black and white developer composition Sodium tetrapolyphosphate 0.5 g Sodium sulfite 25.5 g Potassium carbonate 50.0 g Boric acid
0.7g hydroquinone
10.5 g pyrazone
0.3 g potassium bromide
2. OgPH10,10 [Method A] Add the stock solution of the above black and white developer and water in a ratio of 1=1 to create a developer (
Make PH10,10), put 211 in i-bat and 2
It was developed at 3° C. for 90 seconds, followed by 3 minutes of fixing and 3 minutes of washing. The photosensitive material was cut into eight pieces and processed up to 200 sheets.

[Method B]

In Method A, every 50 pieces of light-sensitive material were processed, hydroxide (+Jum) was added as follows.

2g of NaOH was added to the remaining developer for 0 to 50 sheets (PH was to, io
It was adjusted from 10.30 to 10.30. ).

For 51 to 100 sheets, 2.5 g of Mail was further added to the remaining developer (the pH was adjusted from 10.30 to 10.52).

For 01 to 150 sheets, 3 g of NaOH was further added to the remaining developer (pH was 10.
52 colors 10.741. :It was adjusted. ).

For 51 to 200 sheets, 3 g of Na0)1 was added to the remaining developer (pH was adjusted to 10
．． 74 to 10.941. :,It was adjusted. ).

201-250 sheets An additional 3 g of NaOH was added to the remaining developer.

(The pH was adjusted from 10.94 to 11.13.)

Changes in photographic performance when 251 to 300 sheets were processed using methods A and B are shown below.

In the conventional method (A), it was clearly not possible to obtain the desired photographic performance after processing 150 sheets, but in the present invention (B), the developer could be used with almost no change in photographic performance.

Furthermore, according to the method, when processing 400 to 500 sheets by adding an alkaline agent at a ratio of 3 g of NaOH/50 sheets, although the sensitivity decreased to 1/2, it was found that a sufficient maximum concentration was obtained and it could still be used. Ta. Moreover, in the end, only about 200 ml of black and white developer was used, and the amount of developer that had to be discarded was 10% of the original amount. Therefore, according to the method, it can be considered that the amount of waste liquid is quite close to zero.

Example 2 A multilayer color photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

(Layer structure) The composition of each layer is shown below. The number is the amount of coating per go (g)
It is expressed as For silver halide emulsions and colloidal silver, the amount of coating in terms of silver is expressed in g, and for spectral field-sensitive dyes, the amount added per mole of silver halide is expressed in moles.

The polyethylene on the E1 layer side of the support polyethylene laminate paper contains a white pigment (TiO□) and a bluish dye (ulmarine blue).

81st layer silver halide emulsion 0.26 spectral sensitizing dye (BXSS-1) 1. OX 10-' Spectral sensitizing dye (BxSS-2> 6. I X 10
-' Gelatin 1.11 cyan coupler (εXCC-1) 0.21 cyan coupler (εXCC-1) 0.26 ultraviolet absorber (
BXUV-1) 0.17 solvent (
BXS-L) 0.23 development regulator
(BxGC-1) 0.02 stabilizer (BXA-
1) 0.006 nucleation accelerator (BX7:5-1)
3. QXl 0-'nucleating agent (-1 to BxZ>
8.0X10-' E2 layer gelatin 1.41 Color mixing prevention agent
(ExKB-1> Solvent (BXS-1) Solvent (BxS-2) E3 layer silver halide emulsion spectral sensitizing dye (ExSS-3) Gelatin magenta coupler (1, cMC-1) Color image stabilizer ( BXSA-1) Solvent (BxS-3) Development regulator (BxGC-1) Stabilizer (BXA-1) Nucleation accelerator ([EXZS-1) Nucleating agent (εXCC-1> 84th layer gelatin color mixing prevention) Agent (8X to B-1) Solvent (BXS-1) Solvent (εXS-2) 0.09 0.10 0.10 0.23 3.0X10-' 1.05 0.16 0.20 0. 25 0.02 0,006 2.7X10-'1.4X10-' 0.47 0.03 0.03 0.03 E5 layer colloidal silver gelatin color mixing inhibitor (B-1 in EX) Solvent (BxS- 1) Solvent (BxS-2) 67th layer silver halide emulsion spectral sensitizing dye same as E6 layer 84th layer (BXSS-3) Gelatin yellow coupler (BXYC-1) Solvent (E!X5-2)・Solvent
(ExS-4) Development regulator (BXGC-1) Stabilizer (BXA-1) Nucleation accelerator (BxZS -1) Nucleating agent (BxZK-1) 0.09 0.49 0.03 0.03 0 .03 0.40 4.2X10-' 2.17 0.51 0.20 0.20 0.06 o, o o i 5.0X10-'1.2X10-' 88th layer gelatin 0.54 Ultraviolet absorber ([ExUV-2) 0.21 solvent
(BxS-4) 0.08 E9 layer gelatin 1.28 Acrylic modified copolymer of polyvinyl alcohol, degree of modification 17%) 0.17 Liquid paraffin 0.03 Latex particles of polymethyl methacrylate (average particle size 2. 8 μm) 0.05 81st layer gelatin 8.70 82nd layer The same as E9 layer, in addition to the above composition, gelatin hardening agent BXGK-1
and surfactant were added.

Compounds used to prepare samples (εXCC-1) Cyan coupler (EXCC-2) Cyan coupler (LIC-1) Magenta coupler Yellow coupler (Y-2) (EXSS-3) Spectral sensitizing dye (BxSS-4 ) Spectral sensitizing dye o3- (EXSS-1) Spectral sensitizing dye (εX5S-2) Spectral sensitizing dye (EXS-1) Solvent (EXS-2) Solvent (EXS-3) 1:1 mixture of solvents (by volume ratio) (EXS-4) Solvent 0=P-+0-CsH+5(iso>)+(BXUV
-1) Ultraviolet absorber (EXKB-1) Mixing inhibitor (BXGC-1>Development regulator H (1):(2):(3) 5:3+9 mixture (weight ratio) (ExllV -2) Ultraviolet absorption Agent (1): (2): (3) 2+8:9
Mixture (weight ratio) (ExSA-1) Color image stabilizer (BXA-1) Stabilizer 4-hydroxy-5,6-)limethylene-1°3.3a
, 7-titrazaindene (BxZS-1) Nucleating agent 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride<Fhl-1) Nucleating agent 6-nitoxy thiocarponylamino-2-methyl-1-
Propargyl quinolinium triple oromethanesulfonate (BxGK-1) Gelatin hardener 1-oxy-3,5-dichloro-5-) riazine sodium salt Direct positive silver halide color photosensitive material prepared as above was imagewise exposed with 25DCMS and subjected to the following processing. The processing steps were as follows.

Processing step A Color development 3 minutes 15 seconds 38℃ 350ml/m”
Bleach fixing 90 seconds 38℃ 200mj! /i Stable ■ 20 seconds at 38°C ■ 20 seconds at 38°C The process was carried out in the same manner as in Method A, except that the process was carried out at 38°C.

The replenishment method for the stabilizing bath in Table 1 was a so-called countercurrent replenishment method, in which the stabilizing bath ■ was replenished, the overflow liquid from the stable bath ■ was led to the stable bath ■, and the overflow liquid from the stable bath ■ was led to the stable bath ■. .

However, the processing is done using Fuji Film's color paper processing machine FPR.
P-115 was used, and the slit-type developing tank shown in FIG. 1 was used only for the color development portion (method A). The tank liquid volume of the color developer is 31, and the opening degree of the liquid is approximately 6 x 10 cm.
Met.

Processing step B: Set the replenishment amount of color developer to 1OQmi! /m', and in Figure 1, H and -H3 are refill holes, F1 to F are overflow holes, and the refill method is as shown in the table below.Diethylenetriaminepentaacetic acidbenzylalcoholDiethylene glycolSodium sulfite2.0g 12.8g 3.4g 2.0g 2.0g 14.0g 4.0g 2.0g Sodium Bromide Sulfate Hydroxylamine Sodium Chloride 0, 26g 2, 60g 3, 20g 0, 26g 3.38 Add water 10100O! PH6.5 PH was adjusted with aqueous ammonia or hydrochloric acid.

Potassium carbonate 30.0g 25.0g Add water 1000ml 1
000m 12P H10,2010,40 PH was adjusted with potassium hydroxide or hydrochloric acid.

1-hydroxyethylidene 1.6g1.1' -
Diphosphonic acid (60%) Bismuth chloride polyvinylpyrrolidone ammonia water Nitrilotriacetic acid/3Na 0.35g 0.25g 2.5m 1 1.0g Same as mother liquor Ammonium thiosulfate Sodium bisulfite Diethylenetriamine Pentaacetic acid iron (III) 110g Same as mother liquor 10g 6g ammonium monohydrate Ethylenediaminetetraacetic acid disodium dihydrate g 2-octyl-4-isothiazoline-3-fluorescent brightener (4,4'-diaminostilbene type) Add water to PH 0mg 1, 0g 1000 mβ 7.5 PH was adjusted with potassium hydroxide or hydrochloric acid.

Bleach accelerator 5 x 10-3 mol Methods A and B were run until 86 m of the photosensitive material was processed. With either method, there was no deterioration in photographic properties and the photographic properties could be controlled within the control strips' photographic properties. However, when comparing the total amount of overflow of the color developing solution at this time, it was about 24f for method A, while it was about 2.51f for method B. In other words, by just changing the processing method slightly, The color developer overflow liquid is approximately 1
I was able to reduce it to /10.

[Example 3] Using method B, the replenishment amount was 80 m1/m' and KOH was 1 g Zl.
When the light-sensitive material was processed for 8,600 m'' using methods A and B in the same manner as in Example 2, except that the amount was increased in increments, the same photographic properties were obtained within the control range.

The overflow liquid of method A is approximately 24001 (2,4to
n) B method 〃 〃 is approximately 861 (0,1
ton), and in this case, method B could almost ignore the overflow.

[Brief explanation of the drawing]

FIG. 1 shows a sectional view of a developing device equipped with a slit-like processing path for carrying out the development of the present invention. In the figure, reference numeral 15 indicates a slit-shaped processing path filled with a developer.

Claims (1)

[Claims] When developing exposed silver halide photosensitive materials,
A method for processing silver halide photosensitive materials, characterized by using a developer to which an alkaline agent is added to recover from processing fatigue.