JPH0377941A - Processing method for photosensitive material - Google Patents

Abstract

PURPOSE:To obtain satisfactory physical properties of a film and satisfactory photographic properties even by water-saving washing with a reduced amt. of water by supplying water to the emulsion surface of a washed silver halide photosensitive material immediately before drying. CONSTITUTION:When a silver halide photosensitive material is subjected to prescribed processing such as development, washed and dried, water is supplied to the emulsion surface of the washed photosensitive material immediately before drying to remove chemicals such as a fixing agent in a processing soln. such as a fixing soln. or a bleach-fixing soln. used in a stage before the washing stage and remaining in the emulsion layer from the emulsion layer. Satisfactory physical properties of a film and satisfactory photographic properties are obtd. even by water-saving washing.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a method for processing photosensitive materials.

<Prior art> Silver halide photosensitive materials (hereinafter referred to as photosensitive materials) are
After exposure, it is processed through steps such as development, desilvering, washing with water, and stabilization. A developer is used for development, a bleach solution, a bleach-fix solution, and a fixer are used for desilvering, and tap water or ion exchange water is used for washing.
Stabilizing solutions are used in each stabilization process. The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

Such processing is usually carried out using an automatic processor or the like, and the photosensitive material is sequentially conveyed between processing tanks containing the processing liquid and processed.

In recent years, environmental conservation and
There has been a growing demand for resource conservation, and in particular, conservation of flushing water has become an issue.

This is a long-standing method for saving water for flushing.

A so-called multi-stage countercurrent method (number of stages from 2 to 9) is known, in which a plurality of washing tanks are used and the photosensitive material is sequentially conveyed in a clean direction and washed with water.

In such a multi-stage countercurrent system, when replenishing washing water, the washing water is replenished from the last washing tank, and the overflow from the latter washing tank is sequentially flowed into the preceding washing tank between adjacent washing tanks. It turns out.

<Problems to be Solved by the Invention> As mentioned above, the multi-stage countercurrent method is a typical method for saving washing water, but not only this method but also the amount of washing water used in washing processing in general “
"Water-saving flushing" is desired.

This water-saving washing generally requires less than 400 m! of washing water to replenish per 1 m" of photosensitive material (including rinsing water since it is 0), and the amount of washing water per 1 m" of photosensitive material is 10 to 10 m. It is about 400m1.

In this way, in water-saving washing that uses less water, the fixing process, which is a pre-washing process, removes chemicals such as fixing agents (thiosulfates, etc.) from the processing solution used in the bleach-fixing process. This tends to cause the problem of not being able to be sufficiently washed away from the emulsion layer of the material.

As a result, the physical properties of the film of the photosensitive material after processing may not be sufficient, and images may easily change color or fade.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a photosensitive material in which sufficient film properties and photographic properties can be obtained even during water-saving washing in which the amount of washing water used is reduced.

Means for Solving the Problems> In order to achieve the above object, the present invention has the following configuration (1).
has.

(1) In a method for processing a photosensitive material including a step of drying the silver halide photosensitive material after washing with water, water is applied to the emulsion surface of the silver halide photosensitive material after the water-saving washing and immediately before the drying step. 1. A method for processing a photosensitive material, which comprises:

<Function> In the present invention, a silver halide photosensitive material (hereinafter referred to as a photosensitive material) is subjected to predetermined processing such as development according to its processing steps, and then washed with water and dried.

At this time, since water is applied to the emulsion surface of the photosensitive material in the process after water washing and immediately before drying, the fixer or bleach-fixer used in the process before the water washing process remains in the emulsion layer. The fixing agent and other chemicals in the processing solution are removed from the emulsion layer.

For this reason, the washing process is called "water-saving washing".
Even in this case, the physical properties and photographic properties of the film are sufficient.

Specific composition> Hereinafter, a specific configuration of the present invention will be explained in detail.

FIG. 1 shows an example of the configuration of a photosensitive material processing apparatus (hereinafter abbreviated as the apparatus) for implementing the photosensitive material processing method of the present invention.

The apparatus shown in FIG. 1 subjects color paper P as a silver halide photosensitive material (hereinafter referred to as photosensitive material) to the steps of color development, bleaching and fixing, washing with water, and drying.

The illustrated apparatus has a color developing tank 11 containing a color developing solution 110, a bleach-fixing tank 12 containing a bleach-fixing solution 120, and washing tanks 13 and 14 containing washing water W. A drying chamber 17 for drying the color paper P after washing with water is installed in the stream.

Further, a water application unit 16 is installed downstream of the washing tank 14 and in front of the drying chamber 17 for applying water to the emulsion surface of the color paper P immediately before drying.

The water applying unit 16 has a pair of rollers 16A and 16B, and the roller 16A, which comes into contact with the emulsion surface of the color paper P when it is conveyed, is configured to apply water as shown in FIG. It can be a roller.

In the illustrated example, the color vapor P is transported with its emulsion side facing upward.

However, in the rare case that the color vapor P is transported with the emulsion side facing downward, the roller 16B may be a water application roller having the configuration shown in FIG. 2.

As shown in FIG. 2, such a roller 16A has a roller body 161 with a hollow interior, and water penetrates through the outer peripheral surface and inside of the roller body 161 and flows from the inside of the roller body 161 to the outer peripheral surface. A large number of small holes 1611 are provided so that water seeps out. The size of the small hole 1611 is 0.1 to 2 in diameter.
1111, and the porosity may be about 2.500 to 250.000 pieces/hole.

The material of the roller body is not particularly limited as long as the above structure is possible, and may be any metal such as aluminum, resin, rubber, etc.

Also, a pump 169 is installed, and this pump 16
9 pumps up the water W stored in the container 163,
It is made to be sucked into the roller body 161. The pump 169 also causes water to seep out onto the peripheral surface of the roller by pressure.

Further, it is preferable that an absorbing portion 164 made of a porous material such as a sponge is provided inside the roller main body 161 to facilitate suction of the water W.

Furthermore, it is possible to facilitate the seepage of water onto the emulsion surface of the color vapor P, to uniformly supply water onto the emulsion surface of the color vapor P, and to minimize the amount of water supplied. As shown in the figure, it is preferable that the roller main body 161 also be provided with a covering portion 162 made of a porous material such as sponge, so that the outer circumferential surface of the roller main body 161 is covered with the porous material.

In this case, the water W is brought into contact with the emulsion surface of the color paper P, and the amount of water seeping out onto the circumferential surface of the roller 16A may be about 10 to 120 ml/a'' per unit area of the color vapor P, preferably about 20 to 805 liters. .

Further, the pump 169 may be configured to operate so that the water W is contained in the enveloping portion 162 when the leading end of the color paper P is conveyed to the roller 16A and begins to come into contact with the roller 16A.

On the other hand, the roller 16B paired with the roller 16A is not particularly limited in its structure as long as it rotates in synchronization with the roller 16A and conveys the color vapor P.

Further, this roller 16A has its shaft 165 connected to the side plate 167.
168, and may be driven by a sprocket 166 attached to a shaft 165 in conjunction with another roller 16B (not shown in FIG. 2).

In addition, in Fig. 2, the water W seeps out by providing a small hole 1611, but this is not a limitation. A cylinder or the like coated with a flexible porous member can also be used.

In the present invention, the pair of water application rollers is preferably a pair of nip rollers, and by using the nip rollers, the efficiency of replacing the liquid containing chemicals such as fixing agent contained in the emulsion layer of Color Vapor P with water is improved. do.

Note that the nip pressure in this case may be approximately 50 to 500 g.

In Fig. 1, water washing is carried out using a two-stage countercurrent method in which two washing tanks are installed side by side.In this case, the tank capacity per tank is about 3 to 100β, and the replenishment amount is Color Vapor P.
300 to 4001 per "im", and so-called "water-saving flushing" is performed.

"Water-saving washing" as used in the present invention refers to washing performed by reducing the amount of washing water used for washing, and generally the amount of washing water required for washing per 1 m of photosensitive material is 10 to 400 mJ, preferably 20 to io .

mj, the replenishment amount is 400 m1/m” or less,
Preferably it is 10 to 400 mj/m''.

In addition, the apparatus shown in FIG. 1 is appropriately provided with replenishment tanks for each processing liquid.

Note that the pair of water application rollers 16A and 16B in FIG. 1 may be installed so as to also serve as a crossover for conveying the color paper P from the washing tank 14 to the drying chamber 17.

In the above configuration, the color paper P is in the color developing tank 1.
1. The material is sequentially transported through a bleach-fixing tank 12 and a washing tank 13, 14 for processing.

Immediately before being carried out of the washing tank 14 and reaching the drying chamber 17, the emulsion surface of the color paper P is water W is applied to the drying chamber 1.
7 and dried.

In this case, the amount of water applied to the emulsion surface of the color paper P is 10 to 120 mj, preferably 20 to 80 mj, as described above. By doing so, the liquid containing chemicals such as a fixing agent that still remains in the emulsion layer after washing with water is replaced by water and removed.

In addition, since water is applied using the pair of water application rollers 16A and 16B as described above, the liquid containing the fixing agent etc. is replaced with a small amount of water compared to the case where water is supplied by a shower or the like. In this way, water can be applied without wastage, and there will be no hindrance to the subsequent drying process.

Moreover, since the liquid containing the fixing agent and the like is almost completely removed from the emulsion layer, sufficient drying can be achieved without strict control of the drying temperature.

As described above, since the emulsion layer is dried by washing away the liquid containing the fixing agent, etc., there is no occurrence of reticulation after drying, and the film has sufficient physical properties. In addition, there is no discoloration or fading of the image (the photographic properties are good).

The bleach-fix solution used in the present invention has a fixing agent content of 0.1 to 3 mol, preferably 0.4 to 1.5 mol.
It is preferable to use a thiosulfate such as ammonium thiosulfate as the fixing agent.

The content of such a fixing agent is not limited to the bleach-fixing solution, but may be the same in the fixing solution. The present invention is particularly effective within the above range.

Further, the water used for water application is not particularly limited, and any of tap water, ion-exchanged water, etc. may be used, but it is particularly preferable to use ion-exchanged water.

By using ion-exchanged water, the fixing agent remaining in the emulsion layer can be effectively replaced (and since it is used for processing immediately before the drying process, the heat in the drying chamber is diffused and the rollers are Although it becomes easier to dry, there is an advantage that precipitates are less likely to be generated on the outer circumferential surface of the roller.

Furthermore, if necessary, the water to be applied may contain various additives to be added to the washing water, which will be described later.

In addition, in the case of photosensitive materials for printing, such as color paper as shown in FIG. 1, an aqueous solution containing a compound having an image stabilizing function such as formalin instead of water,
A so-called stabilizing liquid may also be applied.

In this case, it is possible to apply the stabilizing liquid using a pair of rollers, which is preferable from the standpoint of applying the necessary amount of the stabilizing liquid without waste. In addition, by doing this, there is no need to install a new stabilizing bath, and the number of processing baths can be reduced.In addition, since the roller is used for processing immediately before the drying process, Since this roller is also heated, it is possible to react effectively even with a smaller amount of chemical used, and by reducing the amount of chemical used and promoting the reaction, it is possible to improve the physical properties of the film. It will be done. Furthermore, the amount of stabilizing liquid used can be reduced, and the amount of waste liquid can be reduced.

Further, by applying water or a stabilizing liquid using a pair of rollers in this manner, it is possible to obtain an effect equal to or greater than that obtained by adding a new washing tank or stabilizing tank. Furthermore, processing time can be shortened.

In the illustrated example, one pair of water applying rollers is used, but several pairs (2 to 6 pairs) may be used as necessary.

In addition, in the illustrated example, the configuration uses two rinsing tanks, but the configuration is not limited to this, and the number of rinsing tanks can be changed as appropriate. You can also

However, in a configuration in which the stabilizing tank is the final tank, the water applied by the water applying roller is preferably the above-mentioned stabilizing liquid.

Furthermore, the washing process can be performed by applying a processing tank in which processing chambers are connected by narrow passages as described in Japanese Patent Application No. 01-27034 by the present applicant, and in this case, the amount of washing water is significantly reduced. However, when such a washing tank is used and the amount of washing water is less than lOOrag/la",
The present invention is particularly effective.

In Fig. 1, the water application part has a water application port as shown in Fig. 2,
Although the present invention has been described in which a water application roller pair constituted by a roller is applied, the present invention is not limited to such a water application roller, and a water application roller that applies water may also be applied.

Such a water application roller may be any known type, and examples thereof include a roller impregnated with water to apply water, an angle roller, a nip type roller, a kiss coat roller, etc. [5PSE )land
Book (1973)”Processing Me
theds” John Wiley&5ons;S,
L, Hersh, F, Sm1th, Phot, S
ci&Eng, 5(1) 48-54 (1961)
”Rapid Processing: Pr5
ssentSate of the Art'''
″:”Rapid Access Methods
in the United States; J, E, Bates Image Technology
ogy, 14(5), 1O-17 (1972)
”A Review of Processin
Among such application rollers, for example, the one shown in FIG. 3 may be used.

The coating roller shown in FIG. 3 attaches water in a tank to its surface and takes it out, forms a bead between it and the emulsion surface of color paper P, and thereby coats the emulsion surface with water.

As shown in FIG. 3, the application roller 52 has its rotating shaft 54
is pivoted on a machine base (not shown) of the device. Also,
A motor (both not shown) is connected to this rotating shaft 54 via a shaft coupling, and the application roller 52 is rotated in the direction of arrow C by the driving force of this motor.

A part of the application roller 52 is immersed in a tank 55 filled with water W, and when the application roller 52 rotates, the water W is brought out at that point.

The water W taken out by the application roller 52 forms a bead wb between it and the color paper P.
In this state, on the emulsion surface of the color paper P that has been guided and conveyed by the guide plates 51A and 51B,
Coating water is supplied as the color paper P is transported.

In this case, the conveyance speed of color paper P is 5 to 25
It is assumed to be about ts-ls.

Further, a container 53 for supplying water W is installed in the tank 55, and a pump 59 is installed so that water W can be supplied from the container 53 into the tank 55 as needed.

Further, the tank 55 is provided with an overflow port 551 for discharging excess water W stored therein.

Note that when using such a coating roller, it is necessary to convey the color paper P so that the emulsion side of the color paper P is in contact with the coating roller. The direction of the emulsion surface may be controlled so as to be in the above direction by regulating the surface in advance or by installing a roller or the like as appropriate.

The amount of water applied, etc. is the same as in the case of the water application roller pair described above.

In the illustrated example, color paper P is used as the photosensitive material, but it is not limited to color paper, and various color and black and white photosensitive materials can be used.

In addition to color paper, these types of materials include color negative film, color reversal film, color positive film, color reversal photographic paper, photographic light-sensitive materials for plate making, X-ray photographic light-sensitive materials, black-and-white negative film, black-and-white photographic paper, and photosensitive microphotographs. Examples include materials.

In the illustrated example, the processing steps are color development→bleach-fixing→washing→drying, and processing tanks are combined accordingly, but various types can be used depending on the type of photosensitive material.

In addition to the above, such processing steps include, for example, the following.

Constant black and white development → Water washing → Dry color development → Bleaching → Fixing → Water washing → Dry color development → Bleach → Bleach fixing → Water washing → Dry black and white development → Water washing → Reversal processing (fogging sweet exposure or fogging bath treatment → Color development Development a! → Bleach, constant color, washing, drying, black and white development, washing with water, color development, bleaching and fixing, washing with water, drying.

Furthermore, a treatment method may be used in which intermediate water washing is provided in each treatment step.

In addition, various steps such as a pre-hardening bath and a neutralization tower may be combined as necessary.

Alternatively, one-bath development (bleaching) and fixing treatment may be performed.

Note that the water washing treatment in the above step includes a so-called stabilization treatment alone and a treatment combined with the stabilization treatment.

The black and white developer used in the development process in the present invention includes dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). Known developing agents such as the following can be used alone or in combination.

Color developing solutions generally consist of an alkaline aqueous solution containing a color developing agent.

The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N
-ethyl-N-β-methoxyethylaniline, etc.) can be used.

The developer solution may also contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants, and the like.

In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. , an alkaline agent, a solubilizing agent, a surfactant, an antifoaming agent, etc.

The fixing solution or bleach-fixing solution used in the present invention contains a fixing agent.

Examples of fixing agents include thiosulfates such as ammonium thiosulfate, sodium thiosulfate (hypo), sodium ammonium thiosulfate, and potassium thiosulfate, ammonium halides, thioureas, and thioethers. It is preferable to use

In the case of a bleach-fixing solution, it contains a bleaching agent in addition to these fixing agents, and specific examples thereof include iron salts of polycarboxylic acids, red blood salts, bromate compounds, cobalt hexamine, and the like. Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(Ill) ethylenediaminetetraacetate are particularly useful.

In addition to the fixing agent, the fixing solution or bleach-fixing solution can usually contain fixing aids such as preservatives such as sodium sulfite, acid agents, buffers, and hardening agents.

In addition, for bleaching or bleach-fixing solutions, U.S. Patent No. 3,04
No. 2,520, No. 3,241゜966, Special Publication No. 1973
In addition to the bleaching accelerators described in Japanese Patent Publication No. 8506-8506 and Japanese Patent Publication No. 45-8636, and the thiol compounds described in Japanese Patent Application Laid-open No. 65732-1983, various additives can also be added.

The washing water used in the washing step may be tap water, ion-exchanged water, etc., and may contain known additives if necessary.

For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants that prevent the growth of various bacteria and algae, fungicides, hardening agents such as magnesium salts and aluminum salts, drying load, and unevenness. A surfactant or the like can be used to prevent this. Or L, E,
West.

“Water Quality Cr1teria”P
Hot, Sci, and Eng.

vol, 9 No. 6 P341-359 (1965)
Compounds described in et al. can also be used. Furthermore,
In some cases, it may be preferable to add various hardeners used in photographic emulsions disclosed in JP-A-58-13243.

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, fungicides, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

The photosensitive material processing method of the present invention can be applied to any photosensitive material processing apparatus, such as:
Examples include wet copying machines, automatic developing machines, printer processors, video printer processors, coin machines for making photo prints, and color vapor processing machines for plate inspection.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 A color paper, Fuji Rababer Type OIP manufactured by Fuji Photo Film ■, was processed using the apparatus shown in FIG. 1 according to the following processing steps.

Bile L1 Temperature Limb L1 Color development 33℃ 3 minutes 15 seconds 330m
1/s” Bleach-fixing 3G-34℃ 1 minute 30 seconds 330+d/♂22之闳01 01 (Water application) Drying 70±5℃ 1 minute -- Medium)
The water washing mentioned above has the same level of replenishment amount as the processing liquid replenishment amount, and is a water-saving washing method in which the amount of water required for washing is small.

The following treatment liquid was used.

Color paper processing agent cp manufactured by IAri1ken Fuji Photo Film Co., Ltd.
-20 was used.

11n Precept U Supplement] L liquid ammonium thiosulfate 70 mj 100 m1 (7
0%) Sodium metabisulfite 13.3g 16g6
g Anhydrous sodium sulfite rum, 7 g - Ethylenediaminetetraacetic acid ferric ammonium salt 45 g Add 65 g water lj 1 g pH 5,9 ± 0
．． 2 6.5±0.2 Ion-exchanged water was used.

Further, water application in the above step was carried out using a water application roller shown in FIG. 2, the amount of water applied was 60 mj per 1 m'' of color vapor, and ion-exchanged water was used as the water.

Such processing is referred to as processing A.

In Process A, the same process was carried out except that an apparatus to which a coating roller as shown in FIG. 3 was applied instead of the water applying roller as shown in FIG. 2 was used.

The amount of water applied was 90 mj/m''.

This is called process B.

Furthermore, in Process A, the same process was carried out except that a device without a water application section was used.

This is called process C.

Regarding such treatment A%B%C, the occurrence of reticulosis, etc. was investigated.

In treatments A%B, no reticulation occurred (the physical properties of the film were good, and there was no discoloration or fading of the image at all).On the other hand, in treatment C, reticulation occurred.

Example 2 Processes A and B of Example 1 were carried out in the same manner, except that a stabilizing liquid was supplied by a roller instead of water.

In the above, a 10% aqueous solution of 2°4-dichloro-6-hydroxy-1,3,5-triazine sodium salt was used as the stabilizing liquid.

In the second treatment, the same effect as in Example 1 was obtained, and in addition, the same or better effect than in the case of treatment using a stabilizing bath was obtained.

In this treatment, no reticulation occurred even when the drying temperature was raised to 90° C. and the film was dried for 30 minutes.

This is an effect that cannot be obtained with the conventional method using a stabilizing bath, and is thought to be because the application of the stabilizing solution immediately before the drying process effectively improves the physical properties of the film.

Additionally, this eliminates the need to install a new stabilizing bath and reduces the amount of stabilizing solution used.
At the same time, the amount of waste liquid can also be reduced. Furthermore,
Processing time can also be reduced compared to when a new stabilizing bath is installed.

<Effects of the Invention> According to the present invention, a film with sufficient physical properties and photographic properties can be obtained even in so-called water-saving washing.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view showing a configuration example of a photosensitive material processing apparatus according to the present invention. FIG. 2 is a schematic cross-sectional view showing the water application roller applied to FIG. 1. FIG. 3 is a schematic cross-sectional view showing a coating roller applied in the present invention. Explanation of symbols 11...Color developing tank 12...Bleach fixing tank 13.14...Water tank I6...Water application portions 16A, 16B...Water application roller pair 17...Drying chamber 52.・Applying roller

Claims (1)

[Claims] (1) In a method for processing a photosensitive material including a step of drying the silver halide photosensitive material after washing with water, water is applied to the emulsion surface of the silver halide photosensitive material after the water-saving washing and immediately before the drying step. 1. A method for processing a photosensitive material, which comprises: