JPH04323649A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent occurrence of precipitate of silver in a rinsing bath. CONSTITUTION:A device for processing the photosensitive material 1A is formed by arranging bleach-fixing baths 2A, 2B, a control bath 3 containing a control solution 30, rinsing baths 4A, 4B, 4C containing rising water 40 in its order. The control solution 30 contains an antioxidant, such as sulfite, carbonyl bisulfite, alkylsulfic or alkybenzenesulfinic acid. An exposed photosensitive material is developed and dipped into the bleach-fixing solution 20, then dipped into the control solution 30, and then dipped into the rinsing water 40.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic material that has been exposed to light.

0002

[Prior Art] For silver halide photographic materials (hereinafter also simply referred to as photosensitive materials or photosensitive materials) after exposure,
Processing is performed depending on the type. For example, for color photosensitive materials, development, bleaching, fixing (or bleach-fixing)
, water washing treatment is performed sequentially.

[0003] Such processing usually uses a photosensitive material processing device such as an automatic processor, and a developer, bleach, and fixer (or bleach-fixing solution) placed in each of a plurality of processing tanks included in this device. ), by sequentially immersing the photosensitive material in washing water, etc.

[0004] In recent years, the development of small-scale processing systems using small developing machines called minilabs has progressed, and film development and printing can now be done not only in photo labs equipped with large developing machines but also at photo shops. ing.

[0005] In such a small-scale processing system, the challenges include being able to perform processing simply and quickly, achieving high processing efficiency and excellent photographic quality, and miniaturizing the device. Furthermore, from the viewpoint of environmental conservation, etc., it is an issue to further reduce the amount of replenishment of processing liquid and the amount of drained liquid.

As an example of a solution to such problems, the applicant of the present application has developed a method for processing photosensitive materials in a processing tank (hereinafter referred to as a multi-chamber processing tank) consisting of a plurality of processing chambers connected by narrow passages. Discloses a photosensitive material processing apparatus (Japanese Patent Application Laid-Open No.
-205846, 02-267549). According to this device, in each processing chamber, the liquid composition gradient (
concentration gradient) is formed, which improves processing efficiency,
It is possible to reduce the amount of replenishment of the processing liquid and to downsize the device.

By the way, as an invention aimed at improving photographic properties, a photosensitive material of a predetermined composition is processed using two or more bleach-fixing tanks using a counter-current method (the bleach-fixing solution passes through each bleach-fixing tank to the photosensitive material). The silver concentration in the bleach-fix solution in the final bleach-fix tank is 40 to 80% higher than the silver concentration in the bleach-fix solution in the first bleach-fix tank.
% or less (Japanese Patent Application Laid-open No. 64-2047, No. 64-64)
-2048, 64-4744).

However, in this method, the flow of the bleach-fix solution is in a countercurrent manner, so that the processing efficiency is low and the amount of bleach-fix solution to be replenished is large.

[0009] Therefore, the applicant of the present application has provided a blade in each passage in a multi-chamber processing tank, and uses the sealing function of this blade to more reliably maintain the liquid composition gradient (concentration gradient) of the processing liquid in each processing chamber. , by replenishing the processing liquid so that the processing liquid flowing through each processing chamber flows in the same direction as the traveling direction of the photosensitive material (forward flow method), further improving processing efficiency and reducing the amount of processing liquid to be replenished. discloses a photosensitive material processing apparatus capable of
No. 225880).

When this device is applied to bleach-fixing processing,
Since the flow of the bleach-fix solution is in a downward flow system, the silver ion concentration in the bleach-fix solution in the processing chamber increases as the photosensitive material passes through it, and the silver ion concentration in the bleach-fix solution in the processing chamber that the photosensitive material passes through last. The concentration is highest. Therefore, when moving to the next step, rinsing, the amount of silver carried by the photosensitive material into the rinsing tank increases, and silver deposits such as AgBr are formed in the rinsing tank, causing the rinsing tank to become dirty.

In particular, when the washing tank is configured as a multi-chamber processing tank having a blade in each passage as described above, silver deposits adhere to the surface of the blade, staining the blade, and the photosensitive material is deposited between the blades. There is a problem in that when the blade passes through the blade, silver precipitates migrate and adhere to the surface of the photosensitive material, and the silver precipitates also scratch the surface of the blade and the emulsion surface of the photosensitive material.

0012

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing silver halide photographic materials that can prevent the harmful effects of silver precipitates in a washing tank.

[0013]

[Means for Solving the Problems] Such objects are achieved by the present invention as described in (1) to (6) below.

(1) After the exposed silver halide photographic material is developed, it is sequentially passed through a plurality of desilvering processing areas, immersed in a processing solution having at least a fixing ability for desilvering processing, and then , a method for processing a silver halide photographic light-sensitive material in which the material is sequentially passed through a plurality of processing areas for washing, and immersed in washing water for washing, wherein the processing liquid having fixing ability is applied to each of the processing areas for desilvering. is flowing in the same direction as the traveling direction of the silver halide photographic material, and between the desilvering treatment and the water washing treatment, the silver halide photographic material is brought into contact with a conditioning liquid containing an antioxidant. 1. A method for processing a silver halide photographic material, the method comprising:

(2) Among the plurality of desilvering processing regions, the silver ion concentration in the processing solution having fixing ability in the desilvering processing region through which the silver halide photographic light-sensitive material passes last is higher than that of the other processing regions. The method for processing a silver halide photographic material according to (1) above, which has the highest processing area compared to the processing area for desilvering.

(3) The oxidation-reduction potential of the adjustment liquid is -
2. The method for processing a silver halide photographic material as described in 1 or 2 above, wherein the voltage is 250 to -50 mV.

(4) The silver halide photograph according to any one of (1) to (3) above, wherein the desilvering treatment is carried out in a processing tank formed by sequentially connecting a plurality of processing chambers through narrow passages. How to process photosensitive materials.

(5) The silver halide photographic sensitizer according to any one of (1) to (4) above, wherein the water washing treatment is carried out in a processing tank formed by sequentially connecting a plurality of processing chambers through narrow passages. How materials are processed.

(6) The method for processing a silver halide photographic material as described in (4) or (5) above, wherein a blade capable of substantially shielding the passage is installed in the passage.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for processing silver halide photographic materials of the present invention will be explained in detail below with reference to preferred embodiments shown in the accompanying drawings.

FIG. 1 is a cross-sectional side view schematically showing an example of the configuration of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. As shown in the figure, the photosensitive material processing apparatus 1A includes, in order from the left side in the figure, two bleach-fix tanks (desilvering processing area) 2A, 2B, an adjustment tank 3,
Three washing tanks (processing areas for washing) 4A, 4B, and 4C (these are collectively referred to as processing tanks) are arranged in parallel. Although not shown, on the left side of the bleach-fix tank 2A,
At least one developer tank is installed.

The bleach-fix tanks 2A and 2A each contain a processing liquid having a fixing ability up to a predetermined level. As the processing liquid having this fixing ability, a bleach-fixing liquid or a fixing liquid is preferable, and in the illustrated example, a bleach-fixing liquid 2 is used.
0, and will be represented below. In addition, bleach-fix tank 2A
and 2B may both be a fixing tank (in the case of black-and-white processing), a bleaching tank and a fixing tank, a bleaching tank and a bleach-fixing tank, a bleach-fixing tank and a fixing tank, or the like.

A regulating liquid 30, which will be described later, is placed in the regulating tank 3 to a predetermined level.

[0024] In each of the washing tanks 4A, 4B and 4C, a washing tank 40 is filled up to a predetermined level.

Although omitted in the figure, there are rollers and rollers for conveying the photosensitive material S in each of the processing tanks 2A, 2B, 3, 4A, 4B, and 4C and in the upper part between adjacent processing tanks. Guides are installed in predetermined locations. With such rollers and guides, the photosensitive material S is transferred to the bleach-fix tanks 2A, 2B, the adjustment tank 3, the washing tank 4A, as shown by the arrows in FIG.
4B and 4C are conveyed in the order of U-shaped paths, and are immersed in each processing liquid to be processed.

A solution supply port 21 is installed in the bleach-fix tank 2A for supplying a new bleach-fix solution 20, and a solution supply port 21 is installed in the bleach-fix tank 2B for discharging the worn-out and deteriorated bleach-fix solution 20. A drain port 23 is installed. Further, an opening 22 is formed in the tank wall at the boundary between the bleach-fix tanks 2A and 2B.

When new bleach-fix solution is replenished from the solution supply port 21, approximately the same amount of bleach-fix solution 20 in the bleach-fix tank 2A as the refilled amount flows into the bleach-fix tank 2B through the opening 22. Furthermore, approximately the same amount of the bleach-fix solution 20 in the bleach-fix tank 2B is discharged from the drain port 23 by overflow. That is, the bleach-fixing solution 20 flows in the same direction as the traveling direction of the photosensitive material S (downward flow system).

As a result, the desilvering efficiency of the photosensitive material S is improved, and accordingly, the amount of bleach-fix solution 20 to be replenished from the solution supply port 21 can be reduced. Note that such a forward flow method is particularly effective for fixing solutions as well as bleach-fixing solutions.

In this case, the suitable amount of replenishment of the bleach-fixing solution 20 varies depending on the type of photosensitive material S to be processed (for example, film or paper), especially the amount of silver contained in the emulsion layer. For example, in the case of a film such as a color or black negative film, it is preferably about 600 to 1300 ml per 1 m2 of photosensitive material, and when converted to the equivalent of 1 g of silver in 1 m2 of photosensitive material, it is 20 to 260 ml/(Ag1g/m2
). In addition, in the case of photographic paper such as color or black paper, it is preferably about 15 to 120 ml per 1 m2 of photosensitive material, and when converted similarly, it is 15 to 172 ml/(
Ag1g/m2).

[0030] In the present invention, by adopting the above-mentioned downflow method, the bleach-fix solution 20 in the bleach-fix tank 2B contains more silver ions than the bleach-fix solution 20 in the bleach-fix tank 2A. The concentration is high. In this case, the silver ion concentration in the bleach-fixing solution 20 in the bleach-fixing layer 2B is 8 to 20
It is about g/l.

[0031] Inside the adjustment tank 3, a liquid supply port 31 for supplying new adjustment liquid 30 and a liquid drain port 32 for discharging tired and deteriorated adjustment liquid 30 are installed.

When new adjustment liquid 30 is replenished into the adjustment tank 3 from the liquid supply port 31, almost the same amount of tired and deteriorated adjustment liquid 30 as the replenishment amount is discharged from the drain port 32 by overflow. .

The preferred amount of replenishment of the adjustment liquid 30 varies depending on various conditions, but is usually about 15 to 120 ml, particularly about 20 to 60 ml, per 1 m 2 of the photosensitive material to be processed.

A liquid supply port 41 for supplying new washing water 40 is installed in the washing tank 4C, and a liquid drain port 44 for discharging dirty washing water 40 is installed in the washing tank 4A. is set up. Furthermore, openings 42 and 43 are formed in the tank wall at the boundary between the washing tanks 4B and 4C and the tank wall at the border between the washing tanks 4A and 4B, respectively.

When new washing water is replenished from the liquid supply port 41, approximately the same amount of washing water 40 in the washing tank 4C as the replenishment amount is added.
flows into the rinsing tank 4B through the opening 42, and approximately the same amount of rinsing water 40 in the rinsing tank 4B flows into the rinsing tank 4A through the opening 43;
The washing water inside is discharged from the drain port 44 by overflow. That is, the washing water 40 flows in a direction opposite to the traveling direction of the photosensitive material S (countercurrent method).

[0036] As a result, the efficiency of washing the photosensitive material S with water is improved, and accordingly, the amount of replenishment of the washing water 40 from the liquid supply port 41 can be reduced.

In this case, the amount of replenishment of the washing water 40 varies depending on various conditions, but is usually about 15 to 600 ml, more preferably about 15 to 600 ml per m2 of photosensitive material to be processed.
It can be about 60 to 240 ml.

The number of bleach-fix tanks and washing tanks to be installed is not limited to the illustrated example, and two or more adjustment tanks may also be installed.

Next, each processing liquid will be explained.

The bleach-fix solution 20 contains a bleaching agent and a fixing agent.

Examples of bleaching agents include iron (III),
Compounds and complex salts of polyvalent metals such as cobalt (III), chromium (VI), and copper (II), peracids, quinones, nitro compounds, and the like are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3 -Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or citric acid,
Complex salts such as tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, iron(II) ethylenediaminetetraacetate
I) Aminopolycarboxylic acid iron (II) including complex salts
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The content of bleach in the bleach-fix solution 20 is not particularly limited, but is about 0.05 to 1 mol/l, particularly 0.05 to 1 mol/l.
It is preferably about 1 to 0.5 mol/l.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, large amounts of iodide salts, etc., but thiosulfates are common, and thiosulfates are particularly Sodium and ammonium thiosulfate are the most typical.

The content of the fixing agent in the bleach-fixing solution 20 is not particularly limited, but is approximately 0.1 to 4 mol/l, particularly 0.2
It is preferable to set it to about 2 mol/l.

The pH of the bleach-fixing solution 20 is 3.
It is preferably about 5 to 8.5, particularly about 4.5 to 8.0.

The adjustment liquid 30 contains an antioxidant (reducing agent). The photosensitive material S pulled up from the bleach-fix tank 2B is filled with a bleach-fix solution 2 containing a relatively high concentration of silver ions.
However, before entering the washing tank 4A, it is immersed in the adjustment solution 30, and due to the action of the antioxidant, even if silver thiosulfate is diluted with water, silver is not easily liberated. Precipitation of silver in the wash water 40 in 4A to 4C is prevented.

Further, since no silver precipitates are formed in the washing water 40, there is less residual color in the photosensitive material S after washing, and the amount of washing water to be replenished can be further reduced. There are also secondary effects.

Antioxidants in the adjustment solution 30 include sulfites such as sodium sulfite, ammonium sulfite, and potassium sulfite, bisulfites such as ammonium bisulfite and potassium bisulfite, formaldehyde bisulfite, and succinic aldehyde bisulfite. carbonyl bisulfite, such as ethyl sulfinic acid, alkyl sulfuric acid, such as propyl sulfinic acid, alkyl benzene sulfinic acid, such as benzene sulfinic acid, toluene sulfinic acid, benzenedisulfinic acid,
Examples include amines such as triethanolamine and diethanolamine, and one or more of these may be used in any combination.

The content of the antioxidant in the adjustment liquid 30 in the adjustment tank 3 varies depending on various conditions, but is usually between 0.001 and 30%.
It is preferably about 1 mol/1, particularly about 0.01 to 0.1 mol/1.

Note that the bleach-fix solution 20 also contains the same components as the antioxidant, and the bleach-fix solution 20 is brought into the adjustment tank 3 by the photosensitive material S, but the amount brought in is very small. Therefore, it is necessary to actively add antioxidant to the adjustment tank 3 to maintain the above content.

Further, the oxidation-reduction potential of the adjustment liquid 30 is -2
It is preferably about 50 to -50 mV, particularly about -200 to -100 mV. If the redox potential is less than -250 mV, silver ions in silver thiosulfate are reduced and a precipitate is formed, and if it exceeds -50 mV, silver thiosulfate is liberated and precipitates as silver or silver sulfide. It is from.

[0052] As a method for measuring this oxidation-reduction potential, for example, a method of inserting a platinum electrode into a PH meter (Castany LAB, M series M-13 manufactured by Horiba, Ltd.) and measuring ORP (oxidation-reduction potential). can be mentioned.

[0053] As the washing water 40, tap water, ion exchange water, distilled water, etc. are used.

Note that the washing water in the present invention is a concept that includes not only washing water in a narrow sense but also a stabilizing liquid to which a stabilizer has been added.

Examples of the stabilizer include aldehyde compounds typified by formalin, buffers for adjusting the pH of the membrane suitable for dye stabilization, and ammonium compounds.

The washing water 40 contains, for example, various disinfectants, antibacterial agents, antifungal agents, surfactants, optical brighteners, hardeners, chelating agents, compounds of magnesium and bismuth, and decolorizing agents. Various additives may be added.

[0057] Among these, disinfectants, antibacterial agents, and antifungal agents are described in the literature "L.F. West." Water Qu.
ality Criteria” Photo.
Sci. & Eng. Vol. 9 No. 6 (19
65), M. W. Beach, “Microbio
Logical Growth in Motion
-picture Processing” SMPT
E Journal Vol. 85, (1976),
R. O. Deegan, “Photo Proce
ssing Wash Water Biocides
"J. Imaging Tech10, No.6
(1984)”, Japanese Patent Publication No. 57-8542, 57-
No. 58143, No. 58-105145, No. 57-13
No. 2146, No. 58-18631, No. 57-9753
No. 0, No. 57-157244, etc., the literature "Author: R.T. Kreiman, J.Imag
e. Tech 10, (6) p. 242 (1984), isothiazoline compounds described in the literature “Resea
rch Disclosure Volume 205, No.
20526 (May 1981 issue)” and “Issue No. 2
Volume 28, No. 22845 (April 1983)
Isothiazoline compounds described in ”, JP-A-62
- Compounds described in No. 209532, "Chemistry of Bacterial and Bacterial Prevention" by Hiroshi Horiguchi, Sankyo Publishing (1982), "Handbook of Bacterial and Bacterial Technology", Japanese Society of Bacterial and Bacterial Prevention, Hakuhodo (1988) Examples include compounds such as those described above.

The pH of such washing water 40 is 5 to 9.
It is preferably about 5, particularly about 6 to 8.5.

The composition of the developer (particularly the color developer) not shown in the figure is not particularly limited, but is preferably an alkaline aqueous solution containing an aromatic primary amine developing agent as a main component.

The developing agent is preferably a p-phenylenediamine compound, and a typical example is 3-methyl-
4-amino-N,N-diethylaniline, 3-methyl-
4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 3-methyl-4-amino-N-ethyl-N
-(β-methanesulfonamidoethyl)aniline, 3-
Methyl-4-amino-N-ethyl-N-(β-methoxyethyl)aniline and their sulfates, hydrochlorides, phosphates or p-toluenesulfonates, as well as hydrates of these salts, etc. Can be mentioned.

[0061] The developer may also contain alkali metal carbonate,
pH buffering agents such as borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds; hydroxylamine, triethanolamine, diethylhydroxylamine , catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2,2,2]octane), preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol,
Quaternary ammonium salts, amines, thiocyanates, 3,
Development accelerators such as 6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents. ; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-1987-195
Aminopolycarboxylic acid represented by the compound described in No. 845, 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclosure No. 18170 (1
Aminotris (May 979), an organic phosphonic acid described in
methylenephosphonic acid), ethylenediamine-N,N,N
Aminophosphonic acids such as ',N'-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-427
No. 30, No. 54-121127, No. 55-4024, No. 55-4025, No. 55-126241, No. 5
No. 5-65955, No. 55-65956 and Research Disclosure 18170 (May 1979)
It may also contain a chelating agent such as the phosphonocarboxylic acids described.

The content of the developing agent in the developer is not particularly limited, but is approximately 0.1 to 100 mol/l, particularly 0.5 to 100 mol/l.
It is preferably about 30 mmol/l.

[0063] The pH of such a developer is usually 7 or more, most commonly about 9 to 13.

FIG. 2 is a cross-sectional side view schematically showing another example of the configuration of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. Hereinafter, descriptions of the same configurations as the photosensitive material processing apparatus 1A will be omitted, and differences will be described.

The photosensitive material processing apparatus 1B shown in FIG. 2 is equipped with a bleach-fix tank 5 in which a plurality of processing chambers are successively connected through narrow passages in place of the bleach-fix tanks 2A and 2B.

The bleach-fixing tank 5 has a tank main body 51, and inside the tank main body 51, a block-shaped member (hereinafter referred to as a block member) 52 having a desired shape is attached to a rack (not shown). It is inserted in the same state.

Thereby, the five processing chambers 5a, 5b, 5c, 5d, and 5e, which are spaces for desilvering the photosensitive material S, and the narrow width space connecting the processing chambers that are vertically adjacent to each other. Passages 53, 54, 55 and 56 are formed.

[0068] Furthermore, in the upper part of the processing chambers 5a and 5e,
Similar passages 57 and 58 are formed for loading and unloading the photosensitive material S, respectively.

The width (effective slit width) of these passages 53 to 58 is preferably about 5 to 40 times the thickness of the photosensitive material S, that is, about 0.5 to 5 mm. With such a width, the photosensitive material S can be transported without any trouble.

[0070] The length of the passages 53 to 58 is 10 to 200 mm.
, preferably about 20 to 60 mm.

In the illustrated configuration, the volume per processing chamber is approximately 20 to 3000 ml, particularly 100 to 800 ml.
It is preferable to set it to about ml.

The shape and number of processing chambers are not particularly limited, but the number of processing chambers is preferably about 3 to 20, particularly about 5 to 10.

In the bleach-fix tank 5, the photosensitive material S is transported by a transport means (not shown) consisting of rollers, guides, etc. installed in each processing chamber, and passes through a passage 57, a processing chamber 5a, and a passage 53. , processing chamber 5b, passage 54, processing chamber 5c,
The passage 55, the processing chamber 5d, the passage 56, the processing chamber 5e, and the passage 58 are sequentially passed through.

Further, in this bleach-fixing tank 5, as shown by the arrow in FIG. The liquid 20 is discharged from the processing chamber 5e through which the photosensitive material S passes last. Therefore, the bleach-fix solution 20 flows in the same direction as the traveling direction of the photosensitive material S, that is, the processing chamber 5a, passage 53, processing chamber 5b, passage 54, processing chamber 5c, passage 55,
It flows in the order of processing chamber 5d, passage 56 and processing chamber 5e.

In this case, the amount of bleach-fix solution 20 flowing through each passage 53-56 is approximately equal to the replenishment of bleach-fix solution 20, and since each passage 53-56 is narrow, the amount of bleach-fix solution 20 is There is almost no backflow or diffusion of components between adjacent processing chambers, and therefore, in each processing chamber 5a, 5b, 5c, 5d, and 5e, the degree of fatigue and deterioration of the bleach-fix solution increases in this order (silver ion A liquid composition gradient (concentration gradient) is formed and maintained. In this case, the silver ion concentration in the bleach-fix solution 20 in the final processing chamber 5e is about 10 to 40 g/l.

By processing the photosensitive material S in the bleach-fix tank 5 in which such a solution composition gradient is formed, the desilvering efficiency is further improved, and accordingly, the amount of replenishment of the bleach-fix solution 20 is further reduced. be able to. Further, by making the bleach-fixing tank 5 a multi-chamber processing tank as shown in the figure, the apparatus 1B can be downsized.

The constituent materials of the block body 52 include, for example, plastics such as polyethylene, polypropylene, polyphenylene oxide (PPO), ABS resin, phenol resin, polyester resin, and polyurethane resin, ceramics such as alumina, stainless steel, titanium, etc. Examples include hard materials such as various metals. In particular, plastics such as polypropylene, PPO, and ABS resin are preferred because they have excellent moldability, are lightweight, and have sufficient strength.

[0078] Preferably, each passage 53-56 is provided with a blade capable of substantially shielding this passage.

This blade has a block body 5 at its base.
It consists of a thin-walled member fixed to the photosensitive material S, especially a thin-walled member whose thickness gradually decreases toward the tip.
When the blade does not pass, the tips of both blades are in close contact with each other,
Virtually blocks the flow of liquid (sealing function). Also,
When the photosensitive material S passes, the tips of the two blades that are in close contact with each other are pushed apart by the tip of the photosensitive material S, and the photosensitive material S passes between them. At this time, the liquid adhering to the surface of the photosensitive material S is wiped off by sliding with the tip of the blade (squeeze function), and is prevented from being brought into the next processing chamber or the next processing tank.

Examples of the constituent materials of the blade include natural rubber, isoprene rubber, chloroprene rubber, butyl rubber, fluororubber, butadiene rubber, styrene butadiene rubber, ethylene propylene rubber, silicone rubber, chlorosulfonated polyethylene, urethane rubber, and polysulfide rubber. Rubber, various rubbers such as acrylic rubber and epichlorohydrin rubber, silicone resin, soft polyvinyl chloride, polyethylene (especially medium density or low density PE), polypropylene,
Examples include soft resins such as fluororesins, ionomer resins, and elastomers such as Thermolan, Sunplane, Milastomer, and Hytrel.

Even if the photosensitive material S slides on the blade, there will hardly be any adverse effects such as scratches on the emulsion surface, but if this cannot be ignored or if the sliding resistance is to be further reduced, the inside of the blade may be It is also possible to perform a surface treatment such as smoothing the surface or coating it with a lubricant such as fluororesin or polytetrafluoroethylene (Teflon).

The installation angle of the blade (the angle formed with the photosensitive material S) is about 10 to 80 degrees on average, especially about 30 to 60 degrees on average.
It is preferable to set it to about .

[0083] The contact pressure between the blades is 10 to 200
About 0g/cm2, especially 100 to 1000g/cm
It is preferable to set it to about 2. With such a contact surface pressure, even better squeezing and sealing functions can be obtained.

[0084] By installing such blades in each of the passages 53 to 56, the sealing function and squeezing function of the blades are exhibited, and the above-mentioned processing chambers 5a to 5e are
The liquid composition gradient in is maintained even better. In particular, even when the processing of the photosensitive material S is stopped for a long time and then restarted, the composition gradient is maintained, so that good photographic properties can be obtained.

In the photosensitive material processing apparatus 1B, an opening 45 is formed in the tank wall at the boundary between the adjustment tank 3 and the washing tank 4A, and the washing water 40 in the washing tank 4A flows into the adjustment tank 3 through the opening 45. It is designed to flow into the

[0086] Due to the inflow of the washing water 40, the adjustment liquid 30 in the adjustment tank 3 is diluted. Therefore, it is preferable that the adjustment liquid 30 replenished from the liquid supply port 31 be a concentrated adjustment liquid in consideration of this dilution.

Note that in the photosensitive material processing apparatus 1B, the structure of the adjustment tank 3 can be made into a multi-chamber processing tank, and in this case, the adjustment effect is further improved.

FIG. 3 is a cross-sectional side view schematically showing another example of the configuration of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. Hereinafter, descriptions of the same configurations as those of the photosensitive material processing apparatus 1A or 1B will be omitted, and differences will be described.

The photosensitive material processing apparatus 1C shown in FIG. 3 uses the bleach-fix tank 5 and the washing tanks 4A to 4C.
Instead, a washing tank 6 is installed in which a plurality of processing chambers are sequentially connected through narrow passages.

The washing tank 6 has a tank main body 61, and inside the tank main body 61, a block body 62 made of the same material as described above and having a desired shape is attached to a rack (not shown). It has been inserted.

Thereby, five processing chambers 6a, 6b, 6c, 6d and 6e, which are spaces for washing the photosensitive material S, and a narrow narrow space connecting the vertically adjacent processing chambers are formed. Passages 63, 64, 65 and 66 are formed.

[0092] Moreover, in the upper part of the processing chambers 6a and 6e,
Similar passages 67 and 68 are formed for loading and unloading the photosensitive material S, respectively.

It is preferable that the widths (effective slit widths) and lengths of these passages 63 to 68 are the same as those of the passages 53 to 58.

In the illustrated washing tank 6, the volume per processing chamber is approximately 20 to 3000 ml, particularly 80 to 80 ml.
It is preferable to set it to about 0 ml.

In this washing tank 6, the photosensitive material S is transported by a transport means (not shown) comprising rollers, guides, etc. installed in each processing chamber, and is transported through a passage 67 and a processing chamber 6a.
, passage 63, processing chamber 6b, passage 64, processing chamber 6c, passage 65, processing chamber 6d, passage 66, processing chamber 6e, and passage 6
8 in sequence.

Further, in this washing tank 6, as shown by the arrow in FIG. 3, new washing water 40 is supplied to the processing chamber 6e through which the photosensitive material S passes last, and the dirty washing water 40 is transferred The material S is discharged from the processing chamber 6a through which it passes first. Therefore, the washing water 40 flows in the direction opposite to the traveling direction of the photosensitive material S, that is, the processing chamber 6e, the passage 66, the processing chamber 6d, the passage 65, the processing chamber 6c, the passage 64, the processing chamber 6b, the passage 63, and the processing chamber 6a. flows in this order.

In this case, the amount of washing water 40 flowing through each passage 53 to 56 is approximately equal to the amount of replenishment of washing water 40, and since each passage 63 to 66 is narrow, backflow of washing water and There is almost no diffusion of components between adjacent processing chambers, and therefore, in each processing chamber 6a, 6b, 6c, 6d, and 6e, a liquid composition gradient (concentration gradient) in which the degree of contamination of the washing water increases in this order. is formed and maintained.

By processing the photosensitive material S in the washing tank 6 in which such a liquid composition gradient is formed, the washing efficiency is further improved, and accordingly, the amount of replenishment of the washing water 40 can be further reduced. .

Furthermore, by making the bleach-fixing tank 5 and the washing tank 6 into multi-chamber processing tanks as shown in the figure, the apparatus 1C can be further downsized.

[0100] Also in the washing tank 6, each passage 63 to
66 is preferably provided with a blade similar to that described above. Thereby, the sealing function and squeezing function of the blade are exhibited, and the liquid composition gradient in each of the processing chambers 6a to 6e is maintained even better. In particular, even if the processing of the photosensitive material S is stopped for a long time and then restarted,
Since the liquid composition gradient is maintained, good photographic properties can be obtained.

Furthermore, due to the effect of the adjustment liquid 30 as described above, no silver precipitate is generated in the washing tank 6, so that the photographic properties are not adversely affected, and in particular, the silver precipitate does not adhere to the blade. This prevents harmful effects (for example, scratches on the surface of the emulsion of the photosensitive material or the surface of the blade).

[0102] Also in the photosensitive material processing apparatus 1C,
A configuration may be adopted in which the flushing water 40 in the processing chamber 6a flows into the adjustment tank 3.

FIG. 4 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. The photosensitive material processing apparatus 1D shown in the same figure includes an adjustment tank 3 in an adjustment tank 1C.
is omitted, and a bleach-fix tank 5 and a washing tank 6 are installed adjacent to each other. This allows for further miniaturization of the device 1D.

In this photosensitive material processing apparatus 1D, the adjustment liquid 30 is supplied to the processing chamber 6b of the washing tank 6. Then, the mixed liquid of the adjustment liquid 30 and the washing water 40 is supplied to the processing chamber 6c.
is discharged from. Therefore, the processing chamber 6a is filled with the adjustment liquid 30, and this processing chamber 6a mainly functions as the adjustment tank.

FIG. 5 is a cross-sectional side view schematically showing another example of the configuration of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. A photosensitive material processing apparatus 1E shown in the figure is the same as the photosensitive material processing apparatus 1D, except that the supply location of the adjustment liquid 30 is changed.

That is, the adjustment liquid 30 is supplied to the processing chamber 5e of the bleach-fix tank 5. Then, the mixed liquid of the adjustment liquid 30 and the bleach-fix liquid 20 is discharged from the processing chamber 5d. Therefore, the processing chamber 5e is filled with the adjustment liquid 30, and this processing chamber 5e mainly functions as the adjustment tank.

[0107] Note that the photosensitive material processing apparatuses 1D and 1
When replenishing the processing chamber of the multi-chamber processing tank with the adjustment liquid 30 as in E, the replenishment amount is preferably 100% of the replenishment amount.
It can be about 30%, more preferably about 100 to 60%.

FIG. 6 is a cross-sectional side view schematically showing another example of the configuration of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention. The photosensitive material processing apparatus 1F shown in the figure is the same as the photosensitive material processing apparatus 1C, except that the configuration of the adjustment tank 3 is changed.

That is, the adjustment tank 3' in the photosensitive material processing apparatus 1F is of a type in which the photosensitive material S is not immersed in the adjustment liquid, but the adjustment liquid 30 is sprayed onto the photosensitive material S.

As shown in FIG. 6, the bottom of the adjustment tank 3' has a tapered shape, and a drain pipe 34 is connected to the lowest end thereof.

[0111] Further, the adjustment liquid 30 is placed in the upper part of the adjustment tank 3'.
For example, a nozzle 33 is installed to eject water in the form of a shower.

The adjustment liquid 30 ejected from the nozzle 33 is preferably sprayed onto the emulsion surface of the photosensitive material S. After that, the adjustment liquid 30 flows down along the taper at the bottom of the adjustment tank,
The liquid is discharged through the drain pipe 34.

In this case, the amount of the adjustment liquid 30 spouted from the nozzle 33 is about 10 to 20,000 ml/min, particularly about 10,000 ml/min.
It is preferable to set the flow rate to about 0 to 2000 ml/min.

[0114] In such a regulating tank 3', a circulation system may be constructed in which the regulating liquid 30 that has flowed into the drain pipe 34 is returned to the nozzle 33 for reuse. In this case, the amount of adjustment liquid 30 used is further reduced, which is preferable.

[0115] Also in the photosensitive material processing apparatuses 1D, 1E and 1F, it is preferable to install blades 7 similar to those described above in each of the passages 53-56 and 63-66 of the bleach-fixing tank 5 and the washing tank 6. .

In the present invention, the method of bringing the photosensitive material S into contact with the adjustment liquid is not limited to dipping or spraying into the adjustment liquid, but any other method such as coating or spraying may be used.

In the present invention, the type of photosensitive material S to be processed is not particularly limited, and may be either a color photosensitive material or a black and white photosensitive material. For example, color negative film, color reversal film, color positive film, color photographic paper, color reversal photographic paper, photographic material for plate making, X-ray photographic material, black and white negative film, black and white photographic paper, black and white reversal photographic paper, photosensitive material for micro etc.

The present invention is also applicable to various photosensitive material processing apparatuses, such as automatic developing machines, wet copying machines, printer processors, video printer processors, coin machines for making photo prints, and color paper processing machines for plate inspection. be able to.

[0119] Although the present invention has been described above by illustrating configuration examples, the present invention is not limited to these.

[0120]

[Examples] Specific examples of the present invention will be described below.

(Example 1) A photosensitive material processing apparatus having the structure shown in FIG. 1 was manufactured, and using this, a photosensitive material after exposure was subjected to development processing.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

[0123] The development time, bleach-fixing time, adjustment time and washing time were 195 seconds, 240 seconds, and 10 seconds, respectively.
seconds and 120 seconds.

[0124] The replenishment amounts of the developing solution, adjustment solution, and washing water are respectively per 35 mm wide x 24 sheets of photosensitive material.
The volumes were 45 ml, 30 ml, and 50 ml, and the replenishment amount of the bleach-fix solution was 52 ml/(Ag1 g/m2).

(Example 2) A photosensitive material processing apparatus having the structure shown in FIG. 2 was manufactured, and using this, a photosensitive material after exposure was subjected to development processing.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

Further, the development time, fixing time, adjustment time and water washing time were 60 seconds, 120 seconds, 10 seconds and 90 seconds, respectively.

[0128] The replenishment amounts of the developing solution, adjusting solution, and washing water are respectively per 35 mm wide x 24 sheets of photosensitive material.
They were 15 ml, 20 ml, and 100 ml, and the replenishment amount of the fixer was 35 ml/(Ag1 g/m2).

(Example 3) A photosensitive material processing apparatus having the structure shown in FIG. 2 was fabricated, and the photosensitive material after exposure was developed using the apparatus.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

The development time, bleach-fixing time, adjustment time and washing time were 100 seconds, 60 seconds, 10 seconds and 60 seconds, respectively.

[0132] The replenishment amounts of the developing solution, adjustment solution, and washing water are 290 ml and 3 ml, respectively, per 1 m2 of photosensitive material.
0 ml and 364 ml, and the replenishment amount of the bleach-fixing solution was 100 ml/(Ag1 g/m2).

(Example 4) A photosensitive material processing apparatus having the structure shown in FIG. 3 was manufactured, and using this, a photosensitive material after exposure was subjected to development processing.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

The development time, bleach-fixing time, adjustment time and washing time were 45 seconds, 45 seconds, 10 seconds and 90 seconds, respectively.

[0136] The replenishment amounts of the developing solution, adjustment solution, and washing water are 109 ml and 3 ml per 1 m2 of photosensitive material, respectively.
0 ml and 363 ml, and the replenishment amount of the bleach-fixing solution was 60 ml/(Ag1 g/m2).

(Example 5) A photosensitive material processing apparatus having the structure shown in FIG. 4 was manufactured, and using this, a photosensitive material after exposure was subjected to development processing.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

The development time, bleach-fixing time, adjustment time and washing time were 45 seconds, 45 seconds, 10 seconds and 80 seconds, respectively.

The replenishment amounts of the developer, bleach-fix solution, adjustment solution and washing water were the same as in Example 4.

(Example 6) A photosensitive material processing apparatus having the structure shown in FIG. 4 was manufactured, and using this, a photosensitive material after exposure was subjected to development processing.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

The development time, fixing time, adjustment time and water washing time were 60 seconds, 120 seconds, 11 seconds and 90 seconds, respectively.

[0144] The replenishment amounts of the developer, adjustment liquid, and washing water are 15 ml, 20 ml, and 100 ml, respectively, per 24 sheets of 35 mm wide photosensitive material, and the replenishment amount of the fixer is 28 ml/(Ag1g/ m2).

(Example 7) A photosensitive material processing apparatus having the structure shown in FIG. 5 was manufactured, and the photosensitive material after exposure was developed using the apparatus.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

The development time, bleach-fixing time, adjustment time and washing time were 45 seconds, 40 seconds, 5 seconds and 90 seconds, respectively.

[0148] The replenishment amounts of the developer, adjustment solution, and washing water are 15 ml, 20 ml, and 100 ml, respectively, per 24 sheets of 35 mm wide photosensitive material, and the replenishment amount of the bleach-fix solution is 40 ml/(1 g of Ag). /m2).

(Example 8) A photosensitive material processing apparatus having the structure shown in FIG. 6 was fabricated, and the photosensitive material after exposure was developed using the apparatus.

The types of photosensitive materials and the formulations of each processing solution are shown in Table 1 below.

[0151] The development time, bleach-fixing time, adjustment time, and washing time were 195 seconds, 650 seconds, and 20 seconds, respectively.
seconds and 180 seconds.

[0152] The replenishment amount of developer solution and washing water is 36 m per 35 mm wide x 24 sheets of photosensitive material, respectively.
1 and 72 ml, and the replenishment amount of bleach-fix solution is 60 ml.
l/(Ag1g/m2), and the ejection amount of the adjustment liquid is 2
It was set to 0 ml/min.

(Comparative Example) The same procedure as in Example 4 was carried out except that the treatment was carried out with the adjustment liquid in the adjustment tank empty.

[0154]

[Table 1]

Regarding Examples 1 to 8 and Comparative Examples above,
Processing of photosensitive materials is carried out for 10 hours per day.
After the operation continued for a month, the apparatus was stopped and the occurrence of silver precipitates in the washing tank, particularly in the washing tank 4A or the processing chamber 6a, was investigated. Hanakata. In particular, there was no deposit attached to the blade provided in the multi-chamber water washing tank, and therefore no scratches occurred on the emulsion surface of the light-sensitive material.

On the other hand, in the comparative example, a large amount of precipitate was formed, especially in the processing chambers 6b and 6c. In addition, since the precipitate was attached to the blade, the surface of the emulsion of the light-sensitive material was scratched.

[0157]

As described above, according to the method for processing silver halide photographic materials of the present invention, it is possible to prevent the formation of silver precipitates in the washing tank. As a result, good photographic properties are obtained, and scratches on the photosensitive material, blade surface, etc. due to adhesion of silver precipitates are prevented. Furthermore, since no silver deposits are formed, maintenance of the washing tank is easy and the amount of washing water to be refilled can be reduced.Moreover, in light-sensitive materials, sensitizing dyes, dyes, etc. are washed out. There will be less residual color. The present invention particularly includes:
Effective for processing color photosensitive materials with complicated processing steps.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional side view schematically showing a configuration example of a photosensitive material processing apparatus for implementing the method of processing silver halide photographic light-sensitive materials of the present invention.

FIG. 2 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention.

FIG. 3 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention.

FIG. 4 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method for processing silver halide photographic light-sensitive materials of the present invention.

FIG. 5 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method for processing silver halide photographic light-sensitive materials of the present invention.

FIG. 6 is a cross-sectional side view schematically showing another configuration example of a photosensitive material processing apparatus for carrying out the method of processing silver halide photographic light-sensitive materials of the present invention.

[Explanation of symbols]

1A, 1B, 1C, 1D, 1E, 1F Photosensitive material processing equipment 2A, 2B Bleach-fix tank 20 Bleach-fix solution 21 Liquid supply port 22 Opening 23 Drain port 3, 3' Adjustment tank 30 Adjustment liquid 31 Liquid supply port 32 Drain Liquid port 33 Nozzle 34 Drain pipes 4A, 4B, 4C Wash tank 40 Wash water 41 Liquid supply ports 42, 43 Opening 44 Drain port 45 Opening 5 Bleach-fix tank 5a, 5b, 5
c, 5d, 5e processing chamber 51
Tank body 52 Block bodies 53, 54, 55, 56, 57, 58 Passage 6
Washing tanks 6a, 6b, 6c, 6d, 6e Processing chamber 61
Tank body 62 Block bodies 63, 64, 65, 66, 67, 68 Passage S
photosensitive material

Claims (3)

[Claims] Claim 1: After the exposed silver halide photographic material is developed, it is sequentially passed through a plurality of desilvering processing areas,
A method for processing a silver halide photographic material, which comprises immersing it in a processing solution having at least a fixing ability to perform desilvering treatment, and then sequentially passing through a plurality of washing treatment areas, and immersing it in washing water to perform washing treatment, the method comprising: , the processing liquid having fixing ability flows through each of the desilvering processing areas in the same direction as the traveling direction of the silver halide photographic light-sensitive material, and between the desilvering processing and the water washing processing, the processing liquid has the fixing ability. 1. A method for processing a silver halide photographic material, which comprises bringing the silver halide photographic material into contact with a conditioning solution containing an antioxidant. 2. Among the plurality of desilvering processing regions, the silver ion concentration in the processing solution having fixing ability in the desilvering processing region through which the silver halide photographic light-sensitive material passes last is lower than that of other desilvering processing regions. 2. The method for processing a silver halide photographic material according to claim 1, wherein the processing area for silver is highest compared to the processing area for silver. 3. The adjustment liquid has an oxidation-reduction potential of -250.
The method for processing a silver halide photographic material according to claim 1 or 2, wherein the voltage is -50 mV.